- Selective hydrogenation of levulinic acid to valeric acid and valeric biofuels by a Pt/HMFI catalyst
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We describe one-pot high-yield catalytic pathways for the conversion of levulinic acid (LA) to valeric acid (VA) or valeric acid esters (so-called valeric biofuels) under relatively mild conditions (2 or 8 bar H2, 200 °C). A thorough screening study reveals that a HMFI zeolite-supported Pt metal cluster (Pt/HMFI) with an average cluster size of 1.9 nm shows the highest yield of VA (99%) under solvent-free conditions. The use of ethanol or methanol as solvent changes the selectivity, resulting in 81-84% yields of ethyl valerate (EV) or methyl valerate (MV). Pt/HMFI is also effective for selective formation of valeric acid esters from γVL in alcohols under H2. Kinetics, in situ infrared (IR), and acidity-activity relationship studies show a cooperative mechanism of Pt and Bronsted acid sites of HMFI. VA formation from LA can be driven by Pt-catalyzed hydrogenation of LA to γVL, which undergoes proton-assisted ring-opening by HMFI, followed by Pt-catalyzed hydrogenation. Valeric ester formation from LA is driven by esterification of LA to levulinic ester, which is hydrogenated by Pt. the Partner Organisations 2014.
- Kon, Kenichi,Onodera, Wataru,Shimizu, Ken-Ichi
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- Maximising opportunities in supercritical chemistry: The continuous conversion of levulinic acid to γ-valerolactone in CO2
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Phase behaviour is manipulated during the hydrogenation of aqueous levulinic acid in supercritical CO2 to separate almost pure γ-valerolactone from water and unreacted acid with reduced energy requirements compared to conventional processing. The Royal Society of Chemistry.
- Bourne, Richard A.,Stevens, James G.,Ke, Jie,Poliakoff, Martyn
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- Influence of W on the reduction behaviour and Br?nsted acidity of Ni/TiO2catalyst in the hydrogenation of levulinic acid to valeric acid: Pyridine adsorbed DRIFTS study
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Effect of W on 20 wt%Ni/TiO2catalyst is examined in the hydrogenation of levulinic acid (LA) to valeric acid at ambient H2pressure. The interaction between W and Ni had a significant influence on the hydrogenation activity and product selectivity. The H2-TPR (temperature programmed reduction) results emphasized a shift in Tmaxto very high temperatures due to W species which are in close proximity to Ni particles. The N2O decomposition measurements showed a decrease in N2O uptake with the increase in ‘W’ loadings due to a high ratio of Ni2+/Ni0species at higher tungsten content. X-ray photoelectron spectra (XPS) demonstrated a shift in binding energy to higher owing to a strong interaction between W and Ni particles by the presence of ionic Ni at the near surface region. The ionic Ni species seems to be involved in the conversion of γ-valerolactone (GVL) to valeric acid (VA). Pyridine adsorbed infrared (IR) spectra revealed an enormous increase in surface Br?nsted acidity originated from tungsten interacted Ni/TiO2are the sites responsible for ring opening of GVL to form VA.
- Kumar, V. Vijay,Naresh,Deepa,Bhavani, P. Ganga,Nagaraju,Sudhakar,Chary,Venugopal,Tardio,Bhargava
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- Selective and flexible transformation of biomass-derived platform chemicals by a multifunctional catalytic system
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(Figure Presented) A sustainable supply chain: The controlled transformation of the biomassderived platform compounds levulinic acid (LA) and itaconic acid (IA) into the corresponding lactones, diols, or cyclic ethers (see picture) by using a multifunctional molecular catalyst is described.
- Geilen, Frank M. A.,Engendahl, Barhel,Harwardt, Andreas,Marquardt, Wolfgang,Klankermayer, Juergen,Leitner, Walter
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- Enhanced Production of Γ-Valerolactone with an Internal Source of Hydrogen on Ca-Modified TiO2 Supported Ru Catalysts
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Calcium-modified titania supported Ru catalysts were synthesized and evaluated for the hydrogenation of levulinic acid with formic acid as an internal hydrogen source and water as a green solvent. A new elegant photoassisted method was developed for the synthesis of uniform-size and evenly distributed Ru particles on the titania surface. Compared with the counterpart catalysts prepared by classical wet impregnation, enhanced levulinic acid conversion and γ-valerolactone yield were obtained and further improved through modification of the support by introduction of calcium into the titania support. This synthesis approach resulted in a change of the surface and bulk properties of the support, namely a decrease in the anatase crystallite size and the formation of a new calcium titanate phase. As a consequence, the properties of the catalysts were modified, and smaller ruthenium particles that had stronger interactions with the support were obtained. This affected the strength of the CO adsorption on the catalyst surface and facilitated the reaction performance. The optimum size of Ru particles that allowed for most efficient levulinic acid conversion was established.
- Wojciechowska, Joanna,J?drzejczyk, Marcin,Grams, Jacek,Keller, Nicolas,Ruppert, Agnieszka M.
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- Hydrogenation of biomass-derived compounds containing a carbonyl group over a copper-based nanocatalyst: Insight into the origin and influence of surface oxygen vacancies
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New Mn-containing spinel-supported copper nanocatalysts were directly generated via a Cu-Mn-Al layered double hydroxide precursor route and employed in gas-phase hydrogenation of dimethyl succinate (DMS) to γ-butyrolactone (GBL). It was found that the introduction of manganese into catalyst precursors led to the formation of Mn-containing spinel phases, thereby giving rise to highly dispersive Cu0 nanoparticles and a large number of surface defects (i.e., oxygen vacancies (Ov), Mn2+ species) in reduced catalysts. As-formed copper-based nanocatalysts exhibited exceptional catalytic hydrogenation performance with stability enduring up to 100 h. Such high catalytic efficiency could reasonably be attributed to the surface synergism between Mn2+-Ov-Mn2+ defect structures and active metallic copper species, which controlled the key to hydrogenation related to the adsorption of DMS molecules and following activation of carbonyl groups and the dissociation of hydrogen. Most importantly, such copper-based nanocatalysts displayed great potential applications in the hydrogenations of other biomass-derived compounds containing carbonyl groups (e.g., acetol, levulinic acid, levulinic acid esters, and furfural). The present strategy enables us to tune the surface structures of catalysts for designing new type of copper-based catalysts with significantly enhanced catalytic performance.
- Hu, Qi,Yang, Lan,Fan, Guoli,Li, Feng
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- Sustainable Strategy Utilizing Biomass: Visible-Light-Mediated Synthesis of γ-Valerolactone
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A novel sustainable approach to valued γ-valerolactone was investigated. This approach exploits the visible-light-mediated conversion of biomass-derived levulinic acid by using a bimetallic catalyst on a graphitic carbon nitride, AgPd@g-C3N4. Two on one: A novel approach to γ-valerolactone is described that exploits the visible-light-mediated conversion of biomass-derived levulinic acid by using a bimetallic catalyst on graphitic carbon nitride, AgPd@g-C3N4.
- Verma, Sanny,Baig, R. B. Nasir,Nadagouda, Mallikarjuna N.,Varma, Rajender S.
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- A novel hafnium-graphite oxide catalyst for the Meerwein-Ponndorf-Verley reaction and the activation effect of the solvent
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Construction and application of novel hydrogenation catalysts is important for the conversion of carbonyl or aldehyde compounds into alcohols in the field of biomass utilization. In this work, a novel, efficient, and easily prepared hafnium-graphite oxide (Hf-GO) catalyst was constructed via the coordination between Hf4+ and the carboxylic groups in GO. The catalyst was applied into the hydrogenation of biomass derived carbonyl compounds via the Meerwein-Ponndorf-Verley (MPV) reaction. The catalyst gave high efficiency under mild conditions. An interesting phenomenon was found whereby the activity of the catalyst increased gradually in the initial stage during reaction. The solvent, isopropanol, was proved to have an activation effect on the catalyst, and the activation effect varied with different alcohols and temperatures. Further characterizations showed that isopropanol played the activation effect via replacing the residual solvent (DMF) in micro- and mesopores during the preparation process, which was hard to be completely removed by common drying process.
- Li, Xiaomin,Du, Zhengjiang,Wu, Yi,Zhen, Yadong,Shao, Rixin,Li, Bingqi,Chen, Chengmeng,Liu, Quansheng,Zhou, Huacong
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- Conversion of biomass-derived levulinate and formate esters into γ-valerolactone over supported gold catalysts
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The utilization of biomass has recently attracted tremendous attention as a potential alternative to petroleum for the production of liquid fuels and chemicals. We report an efficient alcohol-mediated reactive extraction strategy by which a hydrophobic mixture of butyl levulinate and formate esters, derived from cellulosic biomass, can be converted to valuable γ-valerolactone (GVL) by a simple supported gold catalyst system without need of an external hydrogen source. The essential role of the supported gold is to facilitate the rapid and selective decomposition of butyl formate to produce a hydrogen stream, which enables the highly effective reduction of butyl levulinate into GVL. This protocol simplifies the recovery and recycling of sulfuric acid, which is used for cellulose deconstruction.
- Du, Xian-Long,Bi, Qing-Yuan,Liu, Yong-Mei,Cao, Yong,Fan, Kang-Nian
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- Stabilization of cobalt catalysts by embedment for efficient production of valeric biofuel
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We herein report, for the first time, a bifunctional base-metal catalyst (Co@HZSM-5) that acts as an efficient alternative to noble-metal catalysts (e.g., Pt, Ru) for the conversion of levulinic acid into valeric biofuel under batch and fixed-bed reactor conditions. The cobalt nanoparticles were embedded in HZSM-5 crystals and catalyzed the sequential hydrogenations of the ketone and alkene functional groups; meanwhile, the acidic zeolite catalyzed the ring opening of the γ-valerolactone intermediate. Although base metals (e.g., Co) are abundant and inexpensive, their sintering and/or leaching under liquid-phase conditions always lead to the irreversible deactivation of the catalyst. In this system, the embedment structure stabilizes the nanoparticles, and Co@HZSM-5 could be used up to eight times. This work provides a practical clue toward the stabilization of base-metal catalysts and will inspire the development of large-scale biorefinery.
- Sun, Peng,Gao, Guang,Zhao, Zelun,Xia, Chungu,Li, Fuwei
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- Selective, Heterogeneous Oxidation of Alcohols and Diols with Potassium Permanganate
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Primary alcohols can be conveniently oxidized to carboxylic acids using solid KMnO4/CuSO4*5H2O/KOH in an organic solvent; 1,4- and 1,5-diols can be selectively oxidized to the corresponding lactones using appropriate mixtures of KMnO4/CuSO4*5H2O without added base.
- Jefford, Charles W.,Wang, Ying
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- Domino reaction catalyzed by zeolites with Br?nsted and Lewis acid sites for the production of γ-valerolactone from furfural
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Take the straight path: Furfural was converted into γ-valerolactone (GVL) through sequential transfer-hydrogenation and hydrolysis reactions catalyzed by zeolites with Lewis and Br?nsted acid sites (see picture). Together, Zr-Beta and Al-MFI nanosheets generated GVL in 78 % yield without the use of precious metals or molecular H2. This system offers an attractive streamlined strategy for the production of GVL from biomass-derived molecules. Copyright
- Bui, Linh,Luo, Helen,Gunther, William R.,Román-Leshkov, Yuriy
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- Synergy between the metal nanoparticles and the support for the hydrogenation of functionalized carboxylic acids to diols on Ru/TiO2
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Ruthenium nanoparticles supported on titania are over three times more active than conventional ruthenium on carbon for the hydrogenation of lactic acid. This superior catalytic activity can be due to a combined action of small ruthenium nanoparticles and the titania support.
- Primo, Ana,Concepcion, Patricia,Corma, Avelino
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- Efficient Synthesis of Furfuryl Alcohol and 2-Methylfuran from Furfural over Mineral-Derived Cu/ZnO Catalysts
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Two kinds of typical mineral-derived Cu/ZnO catalysts consisting of aurichalcite and zincian malachite were introduced for furfural hydrogenation to furfuryl alcohol (FOL) and 2-methylfuran (2-MF) in a fixed-bed reactor. Under proper reaction conditions, high yields of FOL (above 99 %) and 2-MF (94.5 %) could be obtained over the aurichalcite Cu/ZnO catalyst (AC-CZ), whereas the best yield of 2-MF was only 76.9 % (0.5 h?1) over the zincian malachite Cu/ZnO catalyst (ZM-CZ). The normalized productivity of 2-MF was 43.5 mol kgCu ?1 h?1 and 17.4 mol kgCu ?1 h?1 for AC-CZ and ZM-CZ, respectively (LHSV=1.5 h?1). The catalysts were characterized by XRD analysis, Raman spectra, CO IR spectroscopy, H2 temperature-programmed reduction, N2O titration, NH3 temperature-programmed desorption, and X-ray photoelectron spectroscopy. The far better performance of AC-CZ in furfural hydrogenation was ascribed to its higher dispersion of copper species, superior copper surface area, better surface acidity distribution, and stronger Cu0–ZnO synergy. In addition, the surface acidity of the catalysts seemed to have a higher influence on 2-MF production than the Cu surface area, but the optimal balance of both factors still needs to be investigated systematically.
- Yang, Xiaohai,Xiang, Xiaomin,Chen, Hongmei,Zheng, Hongyan,Li, Yong-Wang,Zhu, Yulei
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- RANEY Ni catalyzed transfer hydrogenation of levulinate esters to γ-valerolactone at room temperature
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A catalytic transfer hydrogenation process was developed for the production of γ-valerolactone (GVL) from ethyl levulinate (EL) and a H-donor at room temperature. Ethyl levulinate was almost quantitatively converted to γ-valerolactone. Further, a two step process for producing GVL from biomass derived platform molecules was also reported. The Royal Society of Chemistry 2013.
- Yang, Zhen,Huang, Yao-Bing,Guo, Qing-Xiang,Fu, Yao
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- Ruthenium-Promoted Acceptorless and Oxidant-Free Lactone Synthesis in Aqueous Medium
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Ruthenium-catalyzed formation of lactones from diols in aqueous medium has been demonstrated. 1,3,5-Triazaphosphaadamantane (PTA) included water-soluble ruthenium complexes [RuCl 2 (PPh 3)(2,6-Py-(CH 2 -PTA) 2 ]·2Br and [RuCl 2 (PPh 3) 2 (2-PyCH 2 PTA)]·Br in the presence of KOH were found to be efficient for the synthesis of lactones from diols. The reported synthetic protocol is green as it uses water as solvent, avoids the use of any hydrogen acceptor/oxidant, and produces hydrogen as the only side product. Mechanistic studies revealed that lactone formation involved aldehyde intermediate and followed dehydrogenative pathway.
- Bhatia, Anita,Kannan, Muthukumar,Muthaiah, Senthilkumar
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- Single pot conversion of furfuryl alcohol to levulinic esters and γ-valerolactone in the presence of sulfonic acid functionalized ILs and metal catalysts
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Ionic liquids functionalized with acidic anions, HSO4, ClSO 3H, PTSA, TFA (MIm), HSO4 and TFA (NMP) were found to efficiently (99% conversion) catalyze the alcoholysis of furfuryl alcohol (FAL) in the presence of methanol, ethanol, n-butanol and isopropyl alcohol (IPA) to the corresponding levulinic acid esters under mild temperature (90-130 °C) conditions. The extended alkyl chain length of [MIm] using 1,4-butane sultone enhanced the Bronsted acidity of [BMIm-SH][HSO4] catalyst resulting into the highest selectivity of >95% to Me-LA. An increase in both temperature and catalyst concentration increased the furfuryl alcohol conversion and selectivity to levulinate esters. In contrast, an increase in the substrate concentration from 5 to 15% caused a decrease in Me-LA selectivity due to accumulation of intermediate ethers of furfuryl alcohol. Using a combination of [BMIm-SH][HSO4] and 5% Ru/C catalyst, direct conversion of FAL to γ-valerolactone (GVL) is shown for the first time. A complete conversion of FAL with the highest selectivity of 68% to GVL could be achieved under optimum conditions while higher Ru loading enhanced the GVL selectivity to 94% in the hydrogenation step of this tandem approach. Our catalyst system could be efficiently recycled five times retaining the original activity and selectivity levels.
- Hengne, Amol M.,Kamble, Sumit B.,Rode, Chandrashekhar V.
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- Effect of SiO2 support properties on the performance of Cu-SiO2 catalysts for the hydrogenation of levulinic acid to gamma valerolactone using formic acid as a hydrogen source
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Vapor phase catalytic transfer hydrogenation of aqueous levulinic acid (LA) with formic acid (FA) as a hydrogen source was carried out over copper loaded on to several SiO2 supports having different physicochemical properties. The SiO2 supports and Cu-SiO2 catalysts with different support properties were characterized by XRD, TPR, XPS, NH3-TPD and UV-vis techniques to evaluate the copper species and its interaction with the support. The SiO2 support alone showed lower LA conversion and low selectivity to GVL whereas Cu-SiO2 catalysts were found to show high conversion and selectivity to the desired product with formic acid as the hydrogen source. The difference in the activities and product selectivity among different copper supported silica appears to be a complex function of acidity and the nature of copper species in the Cu-SiO2 catalysts. No direct correlation was observed between a specific catalyst property such as acidity and pore size, and the performance of the Cu-SiO2 catalysts. From the characterization, it appears that the species responsible for higher activity and selectivity to GVL are monomeric partially oxidized copper species in a strong interaction with the support in combination with a higher number of acid sites, both of which are present in Cu-SiO2-Q6. Cu-SiO2-Q6 showed the highest conversion and selectivity of 66 and 81%, respectively, under optimized conditions.
- Lomate, Samadhan,Sultana, Asima,Fujitani, Tadahiro
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- Direct catalytic transformation of biomass derivatives into biofuel component γ-valerolactone with magnetic nickel-zirconium nanoparticles
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A series of mixed oxide nanoparticles were prepared by a coprecipitation method and characterized by many techniques. Nickel-zirconium oxide catalysts and their partially reduced magnetic counterparts were highly efficient in the direct transformation of biomass derivatives, including ethyl levulinate, fructose, glucose, cellobiose, and carboxymethyl cellulose, into γ-valerolactone (GVL) without the use of an external hydrogen source, producing a maximum GVL yield of 95.2 % at 200 °C for 3 h with hydrogen-reduced magnetic Zr5Ni5 nanoparticles (-1 h-1). Moreover, the magnetic Zr5Ni5 nanoparticles were conveniently recovered by means of a magnet for five cycles with almost constant activity. Attractive separation: Acid-base bifunctional NiZr nanocatalysts with strong magnetism show high activity and reusability in the transformation of biomass derivatives, including EL, fructose, glucose, cellobiose, and carboxymethyl cellulose, into γ-valerolactone (GVL) with 95.2 % yield and 98 % selectivity (see figure).
- Li, Hu,Fang, Zhen,Yang, Song
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- Selective hydrogenation of levulinic acid to γ-valerolactone using in situ generated ruthenium nanoparticles derived from Ru-NHC complexes
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Hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was studied by using mono- and bidentate p-cymene ruthenium(ii) N-heterocyclic carbene (NHC) complexes as catalyst precursors. In water, all complexes were found to be reduced in situ to form ruthenium nanoparticles (RuNPs) with a high hydrogenation activity. In organic solvents, complexes with monodentate NHC ligands also formed nanoparticles, while complexes with bidentate ligands gave rise to stable homogeneous catalysts with moderate hydrogenation activities.
- Tay, Boon Ying,Wang, Cun,Phua, Pim Huat,Stubbs, Ludger Paul,Huynh, Han Vinh
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- High-yield production of levulinic acid from cellulose and its upgrading to γ-valerolactone
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Direct catalytic conversion of cellulose to levulinic acid (LA) by niobium-based solid acids and further upgrading to γ-valerolactone (GVL) on a Ru/C catalyst were realized through sequential reactions in a reactor. Firstly, using aluminium-modified mesoporous niobium phosphate as a catalyst, cellulose can be directly converted to LA with as high as 52.9% yield in aqueous solution, even in the presence of the Ru/C catalyst. To the best of our knowledge, this is the best result over a heterogeneous catalyst so far. It was found that the type of acid (Lewis and Bronsted acids) and acid strength had an influence on the yield of LA; the doping of aluminium can enhance the strong Lewis and Bronsted acids, especially the strong Lewis acid, thus resulting in the increase of LA yield from cellulose as well as from glucose and HMF. Such an enhancement by a Lewis acid on LA yield from HMF was further confirmed by adding lanthanum trifluoroacetate [(TfO)3La], a strong Lewis acid, in the catalytic system (HCl, (TfO)3H, niobium phosphate), indicating that a suitable ratio of Lewis/Bronsted acid is important for higher selectivity to LA from HMF, as well as from cellulose. Then, after replacing N2 with H2, the generated LA in the reaction mixture can be directly converted to γ-valerolactone through hydrogenation over the Ru/C catalyst without further separation of LA. This journal is the Partner Organisations 2014.
- Ding, Daqian,Wang, Jianjian,Xi, Jinxu,Liu, Xiaohui,Lu, Guanzhong,Wang, Yanqin
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- Simple and efficient conversion of cellulose to γ-valerolactone through an integrated alcoholysis/transfer hydrogenation system using Ru and aluminium sulfate catalysts
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The direct conversion of cellulose to specific chemicals represents an important but challenging area that attracts much attention. In this study, we report, for the first time, a one-step conversion of cellulose to γ-valerolactone (GVL), a platform molecule with multiple applications, by integrating alcoholysis and transfer hydrogenation systems over mixed metal salt and Ru catalysts without external hydrogenation. A maximum GVL yield of 51.2% was obtained at 180 °C for 70 min reaction time with microwave heating. The metal salt effectively catalyzed cellulose alcoholysis to generate levulinate in isopropanol, which was also the hydrogen donor for the subsequent catalytic transfer hydrogenation of levulinate to GVL over the Ru/ZrO2 catalyst. It was found that the types of metal center and support material had a significant influence on the reactivity of the catalyst for the catalytic transfer hydrogenation (CTH) reaction, i.e., concerning the existence of sulfuric acid species and water in the reaction system. Microwave heating was demonstrated to be an effective method for cellulose-to-GVL conversion as compared to conventional oil heating, through drastically reducing the reaction time and avoiding decomposition of the reagents. The catalysts were successfully recycled and reused with high reactivity. Finally, the system was also applied to the synthesis of GVL from real biomass, demonstrating the high applicability and potential of the catalytic system for industrial production.
- Huang, Yao-Bing,Yang, Tao,Luo, Yu-Jia,Liu, An-Feng,Zhou, Yi-Han,Pan, Hui,Wang, Fei
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- In situ generated Ni(0)@boehmite from NiAl-LDH: An efficient catalyst for selective hydrogenation of biomass derived levulinic acid to Γ-valerolactone
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We report in situ generation of Ni(0)@boehmite from NiAl-layered double hydroxide (LDH) under reaction conditions which showed superior catalytic activity in the hydrogenation of levulinic acid (LA) to γ-valerolactone (Gvl) with quantitative yield in aqueous medium. Formation of Ni(0)@boehmite in course of the reaction was confirmed by PXRD, TEM, TGA and FT-IR. This catalyst shows superior conversion compared to a series of simple Ni based homogeneous as well as heterogeneous catalysts. The Ni(0)@boehmite catalyst is recyclable, and active even at higher concentrations of LA (25 wt%).
- Gundekari, Sreedhar,Srinivasan, Kannan
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- Transfer hydrogenation of ethyl levulinate to γ-valerolactone catalyzed by iron complexes
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Conversion of biomass-derived ethyl levulinate to γ-valerolactone is realized by using homogeneous iron-catalyzed transfer hydrogenation (CTH). By utilizing Casey's catalyst and cheap isopropanol as hydrogen source, γ-valerolactone can be generated in 95% yield. Addition of catalytic amount of base is important to achieve good yield.
- Dai, Nan,Shang, Rui,Fu, Mingchen,Fu, Yao
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- Porous Organic Zirconium Phosphonate as Efficient Catalysts for the Catalytic Transfer Hydrogenation of Ethyl Levulinate to γ-Valerolactone without External Hydrogen
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Organic hybrid zirconium phosphonate materials (ZrATMP, ZrEDTMPS, ZrDTPMPA, and ZrHEDP) were synthesized through reaction of organic phosphonic acid sodium salt and ZrOCl2 in water, which exhibited high catalytic activity on the conversion of ethyl levulinate (EL) to γ-valerolactone (GVL) in the presence of isopropanol. The obtained catalysts were characterized by FT-IR, TGA, XRD, BET, XPS, ICP-AES, SEM, TEM, NH3-TPD, and CO2-TPD. The results demonstrate that the number of acid sites and basic sites between the layers of the catalysts play a very important role in promoting the conversion of EL to GVL and that the functional groups that exist in phosphates could regulate the number of acid and basic sites. Meanwhile, the catalysts could be easily separated from the reaction system and reused at least five times without any obvious decrease in activity or selectivity.
- Wang, Jianjia,Wang, Ruiying,Zi, Huimin,Wang, Haijun,Xia, Yongmei,Liu, Xiang
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- Water-promoted hydrogenation of levulinic acid to γ-valerolactone on supported ruthenium catalyst
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A highly efficient and green process for the hydrogenation of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) has been developed. GVL was obtained in a yield of 99.9mol-% with a turnover frequency as high as 7676h-1 in aqueous medium by using a Ru/TiO2 catalyst under mild reaction conditions (70-°C). The strong interaction between Ru and TiO2 facilitated both the dispersion of Ru nanoparticles and the stability of the catalyst. In addition, as solvent, water participated in the hydrogenation of LA, which was confirmed by an isotope- labeling experiment with D (D2O). Specifically, the H atom(s) in water took part in the hydrogenation of the C=O group of LA, which promoted the catalytic activity and GVL yield remarkably. Water of catalysis: Water promotes the hydrogenation of levulinic acid to γ-valerolactone on a supported ruthenium catalyst with a γ-valerolactone yield of 99.9mol-% at 70-°C.
- Tan, Jingjing,Cui, Jinglei,Deng, Tiansheng,Cui, Xiaojing,Ding, Guoqiang,Zhu, Yulei,Li, Yongwang
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- γ-valerolactone ring-opening and decarboxylation over SiO 2/Al2O3 in the presence of water
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γ-Valerolactone (GVL) has been identified as a promising, sustainable platform molecule that can be produced from lignocellulosic biomass. The chemical flexibility of GVL has allowed the development of a variety of processes to prepare renewable fuels and chemicals. In the present work involving a combination of computational and experimental studies, we explore the factors governing the ring-opening of GVL to produce pentenoic acid isomers, as well as their subsequent decarboxylation over acid catalysts or hydrogenation over metal catalysts. The ring-opening of GVL has shown to be a reversible reaction, while both the decarboxylation and hydrogenation reactions are irreversible and kinetically controlled under the conditions studied (temperatures from about 500 to 650 K). The most significant contributor to lactone reactivity toward ring-opening is the size of the ring, with γ- lactones being more stable and less readily opened than δ- and ε-analogues. We have observed that the presence of either a C=C double bond or a lactone (which opens to form a C=C double bond) is necessary for appreciable rates of decarboxylation to occur. Olefinic acids exhibit higher rates of decarboxylation than the corresponding lactones, suggesting that the decarboxylation of alkene acids provides a lower energy pathway to olefin production than the direct decarboxylation of lactones. We observe lower rates of decarboxylation as the chain length of alkene acids increases; however, acrylic acid (3-carbon atoms) does not undergo decarboxylation at the conditions tested. These observations suggest that particular double bond configurations yield the highest rates of decarboxylation. Specifically, we suggest that the formation of a secondary carbenium ion in the β position leads to high reactivity for decarboxylation. Such an intermediate can be formed from 2- or 3-alkene acids which have at least four carbon atoms.
- Bond, Jesse Q.,Martin Alonso, David,West, Ryan M.,Dumesic, James A.
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- MPV reduction of ethyl levulinate to γ-valerolactone by the biomass-derived chitosan-supported Zr catalyst
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Herein, we used the biopolymer chitosan as a support to synthesize a biomass-derived catalyst (chitosan-Zr) to achieve GVL in 97% yield from MPV reduction of EL, by using isopropanol as a hydrogen source. The catalyst system is also applicable to the reduction of various organic compounds with carbonyl groups. Additionally, we have proposed a possible mechanism for this reaction based on the systematic investigation towards the reaction. Moreover, the recycle and reuse experiment showed that this chitosan-Zr exhibited long-life catalytic performance and can maintain its high catalytic performance even after five runs of recycle and reuse experiments.
- Wang, Tianlong,Xu, Hai,He, Jianghua,Zhang, Yuetao
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- Ruthenium p-cymene complexes with α-diimine ligands as catalytic precursors for the transfer hydrogenation of ethyl levulinate to γ-valerolactone
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The ruthenium compounds [(η6-p-cymene)RuCl{κ2N-(HCNR)2}]NO3 (R = 4-C6H4Me, [1]NO3; 4-C6H4OH, [2]NO3; C6H11═Cy, [3]NO3; 4-C6H10OH, [4]NO3; tBu, [5]NO3) were prepared in high yields from [(p-cymene)RuCl2]2, AgNO3 and the appropriate α-diimine. Compounds [2]PF6 and [4]PF6 were obtained by a straightforward reaction of [(η6-p-cymene)RuCl(MeCN)0.66]PF6, [6]PF6, with α-diimine, whereas [4]BPh4 was obtained by metathesis between [4]NO3 and NaBPh4. All the ruthenium products were characterized by analytical methods, IR, NMR and UV-Vis spectroscopy; in addition, the structure of [1]NO3 was ascertained by an X-ray diffraction study. Compounds [1-4]NO3, [4]PF6 and [4]BPh4 were investigated as catalytic precursors in the transfer hydrogenation reaction of ethyl levulinate to γ-valerolactone in isopropanol solution under microwave irradiation. [4]BPh4 was revealed to be the best catalytic precursor, affording γ-valerolactone in 62% yield under optimized experimental conditions.
- Biancalana, Lorenzo,Fulignati, Sara,Antonetti, Claudia,Zacchini, Stefano,Provinciali, Giacomo,Pampaloni, Guido,Raspolli Galletti, Anna Maria,Marchetti, Fabio
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- Conversion of levulinic acid and formic acid into γ-valerolactone over heterogeneous catalysts
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LA Lacers: The conversion of levulinic acid (LA) to γ-valerolactone is catalyzed by heterogeneous catalysts without using the external H2. Ru-P/SiO2 has been demonstrated to be a bifunctional catalyst giving a yield of 96 %. Through a two-step process, excellent performance can be achieved in eight recycling runs. Moreover, no hazardous 2-Me-THF is produced during the process. Copyright
- Deng, Li,Zhao, Yan,Li, Jiang,Fu, Yao,Liao, Bing,Guo, Qing-Xiang
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- An efficient and reusable bimetallic Ni3Fe NPs@C catalyst for selective hydrogenation of biomass-derived levulinic acid to Γ-valerolactone
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Bimetallic nanostructures have attracted great interest as efficient catalyst to enhance activity, selectivity and stability in catalytical conversion. Herein, we report a facile one-pot carbothermal route to in-situ controllable synthesize heterogeneous bimetallic Ni3Fe NPs@C nanocatalyst. The X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and N2 adsorption-description results reveal that the Ni3Fe alloy nanoparticles are evenly embedded in carbon matrix. The as-prepared Ni3Fe NPs@C catalyst shows excellent selective hydrogenation catalytic performance toward the conversion of levulinic acid (LA) to γ-valerolactone (GVL) via both direct hydrogenation (DH) and transfer hydrogenation (TH). In DH of LA, the bimetallic catalyst achieved a 93.8% LA conversion efficiency with a 95.5% GVL selectivity and 38.2 mmol g?1 h?1 GVL productivity (under 130 °C, 2MPa H2 within 2 h), which are 6 and 40 times in comparison with monometallic Ni NPs@C and Fe NPs@C catalysts, respectively. In addition, the identical catalyst displayed a full conversion of LA with almost 100% GVL selectivity and 167.1 mmol g?1 h?1 GVL productivity at 180 °C within 0.5 h in TH of LA. Under optimal reaction conditions, the DH and TH catalytic performance of 500-Ni3Fe NPs@C(3:1) catalyst for converting LA to GVL is comparable to the state-of-the-art noble-based catalysts. The demonstrated capability of bimetallic catalyst design approach to introduce dual-catalytic functionality for DH and TH reactions could be adoptable for other catalysis processes.
- Wang, Haojie,Chen, Chun,Zhang, Haimin,Wang, Guozhong,Zhao, Huijun
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- Vapor-phase hydrogenation of levulinic acid to Γ-valerolactone over Cu-Ni bimetallic catalysts
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Vapor-phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was performed over SiO2-supported Cu-Ni bimetallic catalysts with different Cu/Ni weight ratios under ambient H2 pressure. Characterization of the catalysts was carried out using powder X-ray diffraction, temperature-programmed reduction and thermogravimetric analysis. In contrast to the monometallic catalysts i.e. Ni/SiO2 and Cu/SiO2, the Cu-Ni/SiO2 bimetallic catalyst with a Cu/Ni weight ratio of 6/14 exhibits an excellent catalytic activity, and gave a GVL yield higher than 99% with a productivity of 1.64kgGVLkgcat.?1h?1 at 250°C and at a high WHSV of 1.65h?1 for 50h.
- Yoshida, Rei,Sun, Daolai,Yamada, Yasuhiro,Sato, Satoshi,Hutchings, Graham J.
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- Transfer hydrogenation of methyl levulinate into gamma-valerolactone, 1,4-pentanediol, and 1-pentanol over Cu-ZrO2 catalyst under solvothermal conditions
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Diverse products were obtained from transfer hydrogenation of methyl levulinate (ML) by adjusting different factors under solvothermal conditions. Excellent yields of gamma-valerolactone (GVL, 75%), 1,4-pentanediol (1,4-PDO, 39%), and 1-pentanol (1-PAO, 13.8%) could be obtained using zirconium-supported copper catalyst calcined at 550 °C and under optimal conditions.
- Yang, Yongquan,Xu, Xingliang,Zou, Weijian,Yue, Huijuan,Tian, Ge,Feng, Shouhua
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- Boosting levulinic acid hydrogenation to value-added 1,4-pentanediol using microwave-assisted gold catalysis
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Microwave (MW) -assisted levulinic acid (LA) hydrogenation has been performed over two gold catalysts (commercial 1 wt% Au/TiO2 by AUROlite and 2.5 wt% Au/ZrO2, prepared using deposition-precipitation). MW-assisted LA hydrogenation was carried out in water and in solvent-free conditions via (i) H-transfer and (ii) molecular H2. Au/TiO2 promoted complete LA conversion and the further reduction of the produced GVL to 1,4-pentanediol (1,4-PDO) in the presence of 50 bar H2 at 150 °C (4-hour reaction). Interestingly, selectivity to 1,4-PDO was complete at 200 °C. Extended characterisation highlighted the cooperative role played by the gold nanoparticles and the support, onto which activated hydrogen atoms spillover to react with LA. This results in the remarkable activity of Au/TiO2. Both catalysts showed structural and morphological stability under reaction conditions. It was possible to reactivate the Au/TiO2 catalyst by MW-assisted oxidation, paving the way for catalyst recycling directly inside the MW reactor.
- Bucciol,Tabasso,Grillo,Menegazzo,Signoretto,Manzoli,Cravotto
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- Aqueous Hydrogenation of Levulinic Acid to 1,4-Pentanediol over Mo-Modified Ru/Activated Carbon Catalyst
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A highly efficient and green process was developed for direct conversion of levulinic acid into 1,4-pentanediol over Mo-modified Ru/activated carbon (AC) catalyst in a continuous fixed-bed reactor. The Ru–MoOx/AC catalyst was found to be efficient for the aqueous-phase hydrogenation of levulinic acid to 1,4-pentanediol, whereby a high yield (96.7 mol %) of 1,4-pentanediol was obtained under mild reaction conditions (70 °C, 4 MPa H2).
- Cui, Jinglei,Tan, Jingjing,Zhu, Yulei,Cheng, Fangqin
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- Selective Levulinic Acid Hydrogenation in the Presence of Hybrid Dendrimer-Based Catalysts. Part I: Monometallic
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Hybrid Ru-containing catalysts, based on poly(propylene imine) (PPI) dendrimers, immobilized in silica pores, were synthesized and characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. The synthesized Ru catalysts proved their efficiency in the selective hydrogenation of levulinic acid and its esters at 80 °C, 30 bar of H2, and 50 % volume substrate concentration in water. Quantitative yields of γ-valerolactone were obtained for both micro- and mesoporous Ru catalysts within 2 h with catalytic activity as high as 1610 h?1. The reaction rate and selectivity on γ-valerolactone were found to depend on several factors such as carrier structure, temperature, presence of water, and substrate/Ru ratio. The novelty of these hybrid materials is the presence of both weak acid (SiO2) and organic base centers (dendrimer amino groups), enhancing the dispersion of Ru nanoparticles. The presence of amino groups in the catalyst stabilizes the Ru nanoparticles during the synthesis and promotes the adsorption of levulinic acid on the surface of Ru nanoparticles during the reaction. Synthesized hybrid Ru catalysts can be reused several times without significant loss of activity.
- Maximov, Anton L.,Zolotukhina, Anna V.,Mamedli, Adila A.,Kulikov, Leonid A.,Karakhanov, Edward A.
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- Ruthenium and Iridium Dipyridylamine Catalysts for the Efficient Synthesis of γ-Valerolactone by Transfer Hydrogenation of Levulinic Acid
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The selective and efficient transfer hydrogenation of levulinic acid into γ-valerolactone was performed with new ruthenium and iridium catalysts bearing dipyridylamine (dpa) ligands. Reactions were performed in the presence of formic acid and triethylamine using catalyst loading as low as 0.05 mol % with a ruthenium complex (turnover number = 1980). Recyclability of a ruthenium catalyst was demonstrated by running 6 consecutive reactions in almost quantitative yields.
- Wang, Shengdong,Dorcet, Vincent,Roisnel, Thierry,Bruneau, Christian,Fischmeister, Cédric
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- Conversion of levulinic acid into γ-valerolactone using Fe3(CO)12: mimicking a biorefinery setting by exploiting crude liquors from biomass acid hydrolysis
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The conversion of biomass-derived levulinic acid (LA) into gamma-valerolactone (GVL) using formic acid (FA) and Fe3(CO)12 as the catalyst precursor was achieved in 92% yield. To mimic a biorefinery setting, crude liquor (containing 20% LA) from the acid hydrolysis of sugarcane biomass in a pilot plant facility was directly converted into GVL in good yield (50%), without the need for isolating LA.
- Metzker, Gustavo,Burtoloso, Antonio C. B.
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- Efficient, solvent-free hydrogenation of α-angelica lactone catalysed by Ru/C at atmospheric pressure and room temperature
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The hydrogenation of α-angelica lactone was investigated over Ru/C. A mild protocol was developed, which resulted in full conversion and 96% selectivity toward γ-valerolactone. The reaction network was investigated and α-angelica lactone was employed in the one-pot conversion into 2-methyltetrahydrofuran, demonstrating its superiority as a platform molecule in potential biorefinery schemes. This journal is the Partner Organisations 2014.
- Al-Shaal, Mohammad G.,Hausoul, Peter J. C.,Palkovits, Regina
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- Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium-based metal-organic frameworks
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A series of highly crystalline, porous, zirconium-based metal-organic frameworks (Zr-MOFs) with different ligand functionalities and porosities were applied for catalytic transfer hydrogenation of ethyl levulinate (EL) to form γ-valerolactone (GVL), using isopropanol as a hydrogen donor. The roles of the ligand functionality and the metal center of the Zr-MOFs were identified and reaction parameters optimized, for selective production of GVL. The maximum yield of GVL (up to 92.7%) was achieved in 2 h at 200 °C with UiO-66(Zr). Interestingly, zirconium trimesate (MOF-808) emerged as the most suitable candidate, with the highest GVL formation rate (94.4 μmol g-1 min-1) among the catalysts tested at 130 °C. It was also found to be effective in conversion of EL to GVL in an open system using the solvent refluxing method. Both the catalysts (UiO-66(Zr) and MOF-808) were recycled at least five times under their specified reaction conditions without a notable change in catalytic activity and product selectivity. Fresh and recycled catalysts were characterized in detail using X-ray powder diffraction (XRD), N2 adsorption-desorption, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) in order to understand the stability and structural changes that occurred in the catalysts. Finally, a plausible reaction mechanism was presented on the basis of active sites present in catalysts confirmed by characterization results.
- Valekar, Anil H.,Cho, Kyung-Ho,Chitale, Sachin K.,Hong, Do-Young,Cha, Ga-Young,Lee, U-Hwang,Hwang, Dong Won,Serre, Christian,Chang, Jong-San,Hwang, Young Kyu
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- Production of gamma-valerolactone from sugarcane bagasse over TiO2-supported platinum and acid-activated bentonite as a co-catalyst
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Nowadays, biomass utilization has become the center of attention for researchers worldwide and is driven by the depletion of global petroleum supplies for the production of energy and valuable chemicals while easing the atmospheric CO2 burden. We propose here a green strategy for transforming sugarcane bagasse into gamma-valerolactone (GVL), an attractive platform molecule that can be further converted into a variety of chemical derivatives for wide use in industrial applications. Our recent strategy involves the solid acid-catalyzed hydrothermal conversion of cellulose and hemicellulose derived from biomass to give an aqueous solution comprising levulinic acid (LA), followed by catalytic hydrogenation of LA to GVL. Native and acid-activated bentonites were used as solid acid catalysts to promote hydrothermal conversion of cellulose and hemicellulose. The maximum achievable yield of LA was 159.17 mg per gram of oven-dried biomass for 60 min reaction at 473.2 K in the presence of a 2% acid-activated bentonite catalyst. Catalytic hydrogenation reactions of LA to GVL over 1% Pt@TiO2 and acid-activated bentonite as a co-catalyst were performed at temperatures of 393.2-473.2 K and residence times of 120-360 min. The combined solid catalyst gave an attractive performance with respect to LA conversion (～100%) and GVL selectivity (95%) under milder reaction conditions in comparison to 1% Pt@TiO2 without an acid co-catalyst. The spent catalyst could be reused for five consecutive hydrogenation cycles with a marginal decrease in the catalytic activity and GVL selectivity. Coke formation was believed to be the main cause of catalyst poisoning and calcination of the spent catalyst under a stream of pure oxygen at 723.2 K was applied for removing coke deposits from the active catalyst sites, thus restoring the catalytic performance.
- Putro, Jindrayani N.,Kurniawan, Alfin,Soetaredjo, Felycia E.,Lin, Shi-Yow,Ju, Yi-Hsu,Ismadji, Suryadi
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- Acid-Functionalized Mesoporous Carbon: An Efficient Support for Ruthenium-Catalyzed γ-Valerolactone Production
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The hydrogenation of levulinic acid has been studied using Ru supported on ordered mesoporous carbons (OMCs) prepared by soft-templating. P- and S-containing acid groups were introduced by postsynthetic functionalization before the addition of 1 Ru by incipient wetness impregnation. These functionalities and the reaction conditions mediate the activity and selectivity of the levulinic acid hydrogenation. The presence of S-containing groups (Ru/OMC-S and Ru/OMC-P/S) deactivates the Ru catalysts strongly, whereas the presence of P-containing groups (Ru/OMC-P) enhances the activity compared to that of pristine Ru/OMC. Under mild conditions (70C and 7bar H2) the catalyst shows high selectivity to γ-valerolactone (GVL; >95) and high stability on recycling. However, under more severe conditions (200C and pH2=40bar) Ru/OMC-P is particularly able to promote GVL ring-opening and the consecutive hydrogenation to pentanoic acid.
- Villa, Alberto,Schiavoni, Marco,Chan-Thaw, Carine E.,Fulvio, Pasquale F.,Mayes, Richard T.,Dai, Sheng,More, Karren L.,Veith, Gabriel M.,Prati, Laura
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- Selective hydrogenation of biomass derived substrates using ionic liquid-stabilized ruthenium nanoparticles
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Ionic liquid-stabilized ruthenium nanoparticles with an average size between 2-3 nm are very active catalysts for the hydrogenation of biomass derived substrates. Their catalytic performance complements that of classic homogeneous and heterogeneous ruthenium catalysts.
- Julis, Jennifer,Hoelscher, Markus,Leitner, Walter
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- The transfer hydrogenation of high concentration levulinic acid to γ-valerolactone catalyzed by glucose phosphate carbamide zirconium
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Zr-Based catalysts have been extensively applied in Meerwein-Ponndorf-Verley type catalytic transfer hydrogenation (CTH) reactions, but they are easily deactivated in the CTH conversion of high concentrations of levulinic acid (LA) to γ-valerolactone (γ-GVL). This work discloses that by using cheap glucose and ZrCl4as two main raw materials, glucose phosphate carbamide zirconium (GluPC-Zr) is easily synthesized at large scale and low costviaa simple two-step conversion. The constructed GluPC-Zr has enhanced Lewis acid-base properties and good porosity, thus exhibiting outstanding activity for the CTH reactions of LA or its esters with isopropanol (IPA), providing 95-98% γ-GVL yields. Because of the excellent esterification performance of the introduced acidic phosphate groups, GluPC-Zr also works well at high LA concentrations, achieving a much higher turnover frequency (TOF, 8.2 mmol γ-GVL per g catalyst per h) than previously reported Zr-based catalysts (TOF, 0.2-2.4). And it shows excellent reusability in the reaction of LA with IPA, still providingca.95% γ-GVL yield after the seventh cycle run. This work provides a preferential esterification strategy for LA to hamper catalyst deactivation, which is of special significance for the large-scale production of γ-GVL from biomass-derived LA and a low-cost GluPC-Zr catalyst.
- Chen, Shuainan,Fu, Zaihui,Jiang, Dabo,Liu, Yachun,Wan, Feifei,Yang, Bo,Zhang, Chao,Zhang, Huanhuan,Zhang, Qiao,Zhu, Jiekun
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- A novel and efficient N-doping carbon supported cobalt catalyst derived from the fermentation broth solid waste for the hydrogenation of ketones via Meerwein–Ponndorf–Verley reaction
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Most of the non-noble metal catalysts used for the Meerwein–Ponndorf–Verley (MPV) reaction of carbonyl compounds rely on the additional alkaline additives during preparation to achieve high efficiency. To solve this problem, in this work, we prepared a novel N-doped carbon supported cobalt catalyst (Co@CN), in which the carriers were derived from the nitrogen-rich organic waste, i.e., oxytetracycline fermentation residue (OFR, obtained from oxytetracycline refining workshop). No additional nitrogen sources were used during preparation. The results showed that inherent nitrogen in OFR could provide N-containing basic sites, and formed Co-N structures via coordinating with cobalt. The Co-N sites together with the coexisting Co(0) cooperated to catalyze the conversion of ethyl levulinate (EL) to γ-valerolactone (GVL) by MPV reaction. Co(0) dominated the activation of H in isopropanol, while Co-N dominated the formation of the six-membered ring transition state.
- Chen, Yuxin,He, Runxia,Liu, Quansheng,Yao, Xuefeng,Zhou, Huacong
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- Ru-decorated N-doped carbon nanoflakes for selective hydrogenation of levulinic acid to γ-valerolactone and quinoline to tetrahydroquinoline with HCOOH in water
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The effective dissociation of biomass-derived formic acid, as a sustainable hydrogen source, in water is explored for the hydrogenation of levulinic acid (LA) and quinoline. Ru decorated carbon nanoflakes prepared by carboreduction (in Ar/H2 atmosphere) of Ru containing N-doped carbon were used as catalysts. The successful formation of Ru-decorated N-doped carbons was confirmed by numerous spectroscopic tools. The catalyst exhibited outstanding activity and selectivity for the hydrogenation of LA and quinoline using formic acid as a hydrogen donor in water under mild conditions. The catalyst afforded 99.8% LA conversion and 100% selectivity for γ-valerolactone (GVL), whereas 99.8% quinoline conversion and 93% selectivity for 1,2,3,4-tetrahydroquinoline (THQ) were obtained. Recycling experiments suggested that the catalyst was stable even after the 5 cycles. Various controlled experiments and characterizations were conducted to demonstrate the structure-activity relations and suggest plausible reaction mechanisms for the hydrogenation of LA and quinoline. The exploration of formic acid as a sustainable H2 source and the development of metal decorated N-doped carbons for hydrogenation of LA and quinoline will be fascinating to catalysis researchers and industrialists.
- Chauhan, Arzoo,Kar, Ashish Kumar,Srivastava, Rajendra
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- Sustainable metal-lignosulfonate catalyst for efficient catalytic transfer hydrogenation of levulinic acid to γ-valerolactone
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Production of γ-valerolactone (GVL) from biomass-derived platform levulinic acid (LA) via catalytic transfer hydrogenation (CTH) over renewable lignosulfonate-derived catalyst is reported herein. Lignosulfonate-derived catalysts were prepared by assembled Zr-metals with sodium lignosulfonate (LigS) derived from the industry paper waste. The resulting Zr-LigS catalyst exhibited excellent catalytic performance in 92.5% GVL yield under mild conditions. With the combination of detail catalyst characterizations, catalytic performance of the Zr-LigS catalyst, in-situ ATR-FTIR and poisoning experiments, the hydrothermal treatment of Zr4+ and LigS resulted in the formation of basic sites, which contributed significantly to the CTH reaction. Kinetic experiments demonstrated that the activation energy was as low as 41.9 kJ/mol. Furthermore, isotopic labeling experiments suggested that the β-H in isopropanol is transferred to the C[dbnd]O bond of LA by the formation of six-membered intermediates on the basic sites, which is the rate-determining step.
- Liao, Peizhen,Liu, Qiying,Lu, Luying,Ma, Longlong,Wang, Chenguang,Wu, Jingcheng,Xu, Tianyi,Zhang, Xinghua,Zhu, Yuting
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- Photo-Thermo-Dual Catalysis of Levulinic Acid and Levulinate Ester to γ-Valerolactone
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Herein, we developed photo-Thermo-dual catalytic strategies for the production of γ-valerolactone (GVL) from levulinic acid (LA) and its ester using platinum-loaded TiO2 as a dual-functional catalyst. Both catalytic systems were evaluated under mild reaction conditions. In the photocatalysis system, a base plays crucial roles in the conversion of LA and EL to GVL. The control experiments reveal that plausible mechanistic pathways of both systems proceed via the hydrogenation of the ketone group of LA to the corresponding alcohol as a major intermediate followed by a subsequent cyclization step to GVL. This dual-functional catalyst provides alternative strategies for the conversion of LA and its ester into GVL, which could pave the way for biomass utilization in a more effective and practical manner.
- Bunrit, Anon,Butburee, Teera,Liu, Meijiang,Huang, Zhipeng,Meeporn, Keerati,Phawa, Chaiyasit,Zhang, Jian,Kuboon, Sanchai,Liu, Huifang,Faungnawakij, Kajornsak,Wang, Feng
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p. 1677 - 1685
(2022/01/28)
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- Renewable bio-based routes to γ-valerolactone in the presence of hafnium nanocrystalline or hierarchical microcrystalline zeotype catalysts
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Different renewable bio-based routes leading to the versatile bioproduct γ-valerolactone (GVL) were studied in integrated fashions, starting from furfural (Fur), α-angelica lactone (AnL) and levulinic acid (LA), in the presence of multifunctional hafnium-
- Antunes, Margarida M.,Fernandes, Auguste,Pillinger, Martyn,Ribeiro, Filipa,Silva, Andreia F.,Valente, Anabela A.
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- Regiodivergent Reductive Opening of Epoxides by Catalytic Hydrogenation Promoted by a (Cyclopentadienone)iron Complex
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The reductive opening of epoxides represents an attractive method for the synthesis of alcohols, but its potential application is limited by the use of stoichiometric amounts of metal hydride reducing agents (e.g., LiAlH4). For this reason, the corresponding homogeneous catalytic version with H2 is receiving increasing attention. However, investigation of this alternative has just begun, and several issues are still present, such as the use of noble metals/expensive ligands, high catalytic loading, and poor regioselectivity. Herein, we describe the use of a cheap and easy-To-handle (cyclopentadienone)iron complex (1a), previously developed by some of us, as a precatalyst for the reductive opening of epoxides with H2. While aryl epoxides smoothly reacted to afford linear alcohols, aliphatic epoxides turned out to be particularly challenging, requiring the presence of a Lewis acid cocatalyst. Remarkably, we found that it is possible to steer the regioselectivity with a careful choice of Lewis acid. A series of deuterium labeling and computational studies were run to investigate the reaction mechanism, which seems to involve more than a single pathway.
- De Vries, Johannes G.,Gandini, Tommaso,Gennari, Cesare,Jiao, Haijun,Pignataro, Luca,Stadler, Bernhard M.,Tadiello, Laura,Tin, Sergey
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p. 235 - 246
(2022/01/03)
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- Synthesis and characterisation of a range of Fe, Co, Ru and Rh triphos complexes and investigations into the catalytic hydrogenation of levulinic acid
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The coordination chemistry of the N-triphos ligand (NP3Ph, 1b) has been investigated with a range of Fe, Co and Rh precursors and found to form either tridentate or bidentate complexes. Reaction of NP3Ph with [Rh(COD)(CH3CN)2]BF4 resulted in the formation of the tridentate complex [Rh(COD)(κ3-NP3Ph)]BF4 (3) in the solid state, however, in solution a bidentate complex predominates in more polar solvents. Reaction of NP3Ph with Fe carbonyl precursors revealed the formation of the bidentate complexes [Fe(CO)3(κ1,κ2-NP3Ph)Fe(CO)4] (4) and [Fe(CO)3(κ2-NP3Ph)] (5), while reaction with FeBr2 resulted in the paramagnetic bidentate complex [Fe(Br)2(κ2-NP3Ph)] (6). Reaction of NP3Ph with CoCl2 gave a dimeric Co species [(κ2-NP3Ph)CoCl(κ1,κ2-NP3Ph)CoCl3] (7), while Zn powder reduction of NP3Ph Co halides resulted in the formation of the tridentate complexes of the type: [Co(X)(κ3-NP3Ph)]. The related triphos Ru complex, [Ru(CO3)(CO)(κ3-CP3Ph)] (2), has also been isolated and characterised. Preliminary catalytic hydrogenation of levulinic acid (LA) was conducted with 2 and 3. The Ru complex was found to be catalytically active, giving high conversions of LA to form gamma-vvvalerolactone (GVL) and 1,4-pentanediol (1,4-PDO), while 3 was found to be catalytically inactive. In situ catalytic testing with 1b and Fe(BF4)2.6H2O resulted in low conversions of LA while a combination of 1b and Co(BF4)2.6H2O gave high conversions to GVL.
- Omoruyi, Uwaila,Page, Samuel J.,Apps, Samantha L.,White, Andrew J.P.,Long, Nicholas J.,Miller, Philip W.
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- A nitrogen-doped carbon modified nickel catalyst for the hydrogenation of levulinic acid under mild conditions
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The conversion of levulinic acid (LA) to γ-valerolactone (GVL) is one of the most important reactions from biomass-derived platform chemicals to value-added chemicals. In this work, nitrogen-doped carbon was introduced into a Ni/Al2O3catalyst and was employed for the hydrogenation of LA to GVL with a full conversion and equivalent yield under mild conditions, at as low as ambient hydrogen pressure and 130 °C for 6 h. The doping of nitrogen introduced NiNx species and the imperfection of modified nitrogen-doped carbon were beneficial for the selective hydrogenation of carbonyl groups. This catalyst showed excellent activity and selectivity in various solvents and could be recycled for at least 6 runs with little deactivation. In addition to LA, various substrates with both carbonyl and carboxyl groups could also be selectively hydrogenated to the corresponding lactones. This study offers both theoretical foundation and practical instructions for the high-efficiency conversion of LA to GVL over non-noble metal catalysts under mild conditions, especially ambient H2pressure.
- Fu, Yao,Jiang, Liang,Xu, Guangyue
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p. 7065 - 7073
(2021/09/28)
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- One-pot conversion of furfural to gamma-valerolactone in the presence of multifunctional zirconium alizarin red S hybrid
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A multifunctional Zr-containing catalyst (FM-Zr-ARS) was successfully synthesized by a modulated hydrothermal synthesis route. Systematic characterization results supported the presence of robust porous inorganic-organic frameworks stabilized by the strong coordination interaction of Zr4+ with oxygen-rich functional groups in Alizarin red S (ARS). Moreover, the -O-Zr-O- network in the FM-Zr-ARS structure formed a rich content of acid-base sites. In addition, the inherent sulfonic groups in ARS made the FM-Zr-ARS hybrids possess Br?nsted acid sites. Therefore, under the synergistic catalysis of the multiple functional sites, FM-Zr-ARS showed remarkably high catalytic activity for γ-valerolactone (GVL) production from levulinate esters and furfural. Finally, 72.4 % and 97.7 % yields of GVL were obtained in the conversion of furfural and ethyl levulinate, respectively, after 8 h of reaction at 433 K. On the basis of the role of different functional sites, a plausible catalytic mechanism was presented for the conversion of biomass-derived furfural to GVL.
- Peng, Qingrui,Wang, Haijun,Xia, Yongmei,Liu, Xiang
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- Direct use of the solid waste from oxytetracycline fermentation broth to construct Hf-containing catalysts for Meerwein-Ponndorf-Verley reactions
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The oxytetracycline fermentation broth residue (OFR) is an abundant solid waste in the fermentation industry, which is hazardous but tricky to treat. The resource utilization of the waste OFR is still challenging. In this study, a novel route of using OFR was proposed that OFR was used as the organic ligands to construct a new hafnium based catalyst (Hf-OFR) for Meerwein-Ponndorf-Verley (MPV) reactions of biomass-derived platforms. The acidic groups in OFR were used to coordinate with Hf4+, and the carbon skeleton structures in OFR were used to form the spatial network structures of the Hf-OFR catalyst. The results showed that the synthesized Hf-OFR catalyst could catalyze the MPV reduction of various carbonyl compounds under relatively mild reaction conditions, with high conversions and yields. Besides, the Hf-OFR catalyst could be recycled at least 5 times with excellent stability in activity and structures. The prepared Hf-OFR catalyst possesses the advantages of high efficiency, a simple preparation process, and low cost in ligands. The proposed strategy of constructing catalysts using OFR may provide new routes for both valuable utilization of the OFR solid waste in the fermentation industry and the construction of efficient catalysts for biomass conversion.
- Chen, Yuxin,Yao, Xuefeng,Wang, Xiaolu,Zhang, Xuefeng,Zhou, Huacong,He, Runxia,Liu, Quansheng
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p. 13970 - 13979
(2021/04/22)
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- Ir(triscarbene)-catalyzed sustainable transfer hydrogenation of levulinic acid to γ-valerolactone
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Sustainable iridium-catalyzed transfer hydrogenation using glycerol as the hydride source was employed to convert levulinic acid to γ-valerolactone (GVL) with exceptionally high turnover numbers (TONs) (500,000) and turnover frequencies (TOFs) (170,000 h?1). The highly efficient triscarbene-modified iridium catalysts demonstrated good catalytic activities with low catalyst loadings (0.7 ppm) and good recyclability with an accumulated TON of over two million in the fourth reaction. In addition to glycerol, propylene glycol (PG), ethylene glycol (EG), isopropanol (IPA), and ethanol (EtOH) successfully transferred hydrides to levulinic acid, producing GVL with TONs of 339,000 (PG), 242,000 (EG), 334,000 (IPA), and 208,000 (EtOH), respectively. Deuterium-labeling experiments were conducted to gain insight into the reaction mechanism.
- Sung, Kihyuk,Lee, Mi-hyun,Cheong, Yeon-Joo,Jang, Hye-Young
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- Efficient single-atom Ni for catalytic transfer hydrogenation of furfural to furfuryl alcohol
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The employment of single-atom catalysts in the catalytic transfer hydrogenation (CTH) of furfural (FF) to furfuryl alcohol (FAL) has never been effectively explored. Herein, a catalyst of Ni single-atoms supported on nitrogen doped carbon (Ni-SAs/NC) is synthesized and first ever utilized in the CTH of FF to FAL. Atomically dispersed Ni-N4 sites change the electron density at the metal center and exhibit specific adsorption and desorption to FF and FAL, promoting an outstanding catalytic performance with a turnover frequency (TOF) of 832 h-1 and selectivity as high as 97.1% at 130 °C for 2 h. Such performance is 9-fold higher than that of supported Ni nanocatalysts. The Ni-SAs/NC catalyst also exhibits superior stability for the CTH of FF and excellent catalytic activity for other α,β-unsaturated aldehydes. This work provides a new strategy of producing green chemical compounds using catalytic biomass conversion and suggests the future application of long-lasting single-atom catalysts for emerging sustainable technologies.
- Fan, Yafei,Zhuang, Changfu,Li, Shangjing,Wang, Ying,Zou, Xiaoqin,Liu, Xiaoteng,Huang, Weimin,Zhu, Guangshan
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p. 1110 - 1118
(2021/01/25)
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- Highly efficient Meerwein-Ponndorf-Verley reductions over a robust zirconium-organoboronic acid hybrid
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The Meerwein-Ponndorf-Verley (MPV) reaction is an attractive approach to selectively reduce carbonyl groups, and the design of advanced catalysts is the key for these kinds of interesting reactions. Herein, we fabricated a novel zirconium organoborate using 1,4-benzenediboronic acid (BDB) as the precursor for MPV reduction. The prepared Zr-BDB had excellent catalytic performance for the MPV reduction of various biomass-derived carbonyl compounds (i.e., levulinate esters, aldehydes and ketones). More importantly, the number of borate groups on the ligands significantly affected the catalytic activity of the Zr-organic ligand hybrids, owing to the activation role of borate groups on hydroxyl groups in the hydrogen source. Detailed investigations revealed that the excellent performance of Zr-BDB was contributed by the synergetic effect of Zr4+and borate. Notably, this is the first work to enhance the activity of Zr-based catalysts in MPV reactions using borate groups.
- Song, Jinliang,Hua, Manli,Huang, Xin,Visa, Aurelia,Wu, Tianbin,Fan, Honglei,Hou, Minqiang,Zhang, Zhaofu,Han, Buxing
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supporting information
p. 1259 - 1265
(2021/02/26)
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- Zirconium-Gallic Acid Coordination Polymer: Catalytic Transfer Hydrogenation of Levulinic Acid and Its Esters into γ-Valerolactone
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The conversion of ethyl levulinate (EL) to produce γ-valerolactone (GVL) through catalytic transfer hydrogenation (CTH) reaction plays a crucial role in the field of biomass catalytic conversion. In this work, a novel Zr-base catalyst with phenate group, phenolic hydroxyl and carboxyl in its structure was prepared by the co-precipitation of natural sources gallic acid and ZrCl4. It was found that Zr-GA has an excellent catalytic performance for this reaction and satisfactory GVL yield could be achieved. Besides, Zr-GA could be easily separated from the reaction system and reused at least six times without a significantly decrease in activity. Meanwhile, various characterizations had proved that Zr-GA is a porous material with acid–base bifunctional sites. The main reason for the high catalytic activity of the Zr-GA was that the synergetic effects of Lewis acid/base sites and Br?nsted acid sites and appropriate textural properties. In addition, a possible reaction mechanism was proposed in conjunction with the poisoning experiment and previous reports. The heterogeneous catalyst Zr-GA prepared with gallic acid as a raw material has low cost and recyclability, and has great potential in green chemistry. Graphical Abstract: [Figure not available: see fulltext.]
- Li, Xiaoning,Li, Yehui,Wang, Haijun,Wang, Xiang
-
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- Efficient hydrogenation of levulinic acid catalysed by spherical NHC-Ir assemblies with atmospheric pressure of hydrogen
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A practical, efficient, and mild hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) under 1 atm H2was realized by single-sited 3D porous self-supported N-heterocyclic carbene iridium catalysts. Quantitative yields and selectivities were achieved at 0.02 mol% catalyst loading, and the catalyst could be reused for 9 runs without obvious loss of selectivity or activity.
- Liu, Yaoqi,Lu, Zeye,Shen, Lingyun,Tu, Tao,Wu, Jiajie,Zheng, Qingshu
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supporting information
p. 5037 - 5042
(2021/07/29)
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- Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over supported MoS2catalysts
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The hydrogenation of levulinate esters to γ-valerolactone (GVL) is an important step in the transformation of biomass into biofuels. It is attractive to develop new efficient systems for the catalytic transfer hydrogenation (CTH) of levulinate esters to value-added GVL. In this work, a series of MoS2-based supported catalysts were prepared via an impregnation method for the CTH of biomass-derived ethyl levulinate (EL) to GVL. By comprehensive characterization and catalytic measurements, we found that the CTH activity of EL to GVL is closely related to the MoS2 morphology and acid distribution on the support. Among the catalysts with different supports, the AC support with abundant Lewis acid sites and large surface area facilitated the high dispersion of low stacked MoS2 slabs, and the MoS2-acid synergistic catalysis contributed to the superior activity and selectivity. The conversion of EL and the selectivity of GVL reached 97.2% and 91.2% under optimized conditions over the MoS2/AC catalyst (230 °C, 1 MPa H2, 1.5 h), respectively. We also conducted reaction kinetic experiments to reveal the relationship between the active site of the MoS2/AC catalyst and its catalytic performance, and the plausible reaction pathway and mechanism over MoS2/AC was proposed. The catalytic performance gradually declined during recycling tests due to the oxidation of MoS2 and can be easily recovered by resulfuration.
- Diao, Xinyong,Ji, Na,Jiang, Sinan,Liu, Caixia,Liu, Qingling,Liu, Zhenyu,Lu, Xuebin,Ma, Degang,Song, Chunfeng,Yu, Zhihao
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p. 5062 - 5076
(2021/08/16)
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- Zeolite-Tailored Active Site Proximity for the Efficient Production of Pentanoic Biofuels
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Biofuel production can alleviate reliance on fossil resources and thus carbon dioxide emission. Hydrodeoxygenation (HDO) refers collectively to a series of important biorefinery processes to produce biofuels. Here, well-dispersed and ultra-small Ru metal nanoclusters (ca. 1 nm), confined within the micropores of zeolite Y, provide the required active site intimacy, which significantly boosts the chemoselectivity towards the production of pentanoic biofuels in the direct, one-pot HDO of neat ethyl levulinate. Crucial for improving catalyst stability is the addition of La, which upholds the confined proximity by preventing zeolite lattice deconstruction during catalysis. We have established and extended an understanding of the “intimacy criterion” in catalytic biomass valorization. These findings bring new understanding of HDO reactions over confined proximity sites, leading to potential application for pentanoic biofuels in biomass conversion.
- Chen, Shaohua,Chen, Tiehong,Chu, Shengqi,Gu, Qingqing,He, Jiang,Liu, Yuanshuai,Luo, Wenhao,Wang, Aiqin,Weckhuysen, Bert M.,Wu, Zhijie,Yang, Bing,Zhang, Tao,Zhang, Yafeng
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supporting information
p. 23713 - 23721
(2021/09/22)
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- Selective production of γ-valerolactone and ethyl valerate from ethyl levulinate using unsupported nickel phosphide
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Unsupported nickel phosphide catalyst containing Ni2P phase was applied in the hydrodeoxygenation of ethyl levulinate in ethanol medium for the first time. The obtained catalyst was investigated by XRF, XRD, NH3–TPD, XPS and TEM techniques. γ-valerolactone and ethyl valerate were obtained as the hydrodeoxygenation products. Varying the temperature and the reaction time it was possible to obtain these products with high selectivity. γ-valerolactone was selectively formed at 200–250 °C and ethyl valerate was selectively formed at temperatures of 300–350 °C. Increase in reaction time was contributed to ethyl valerate formation. The highest selectivity of ethyl valerate was 100% at full ethyl levulinate conversion at 350 °C after 6 h. 100% γ-valerolactone selectivity was reached at low conversion of ethyl levulinate. The highest yield of γ-valerolactone reached 41.7% after 6 h of the reaction at 250 °C. The selectivity of γ-valerolactone was 86.9% and the conversion of ethyl levulinate was 48.0%.
- Golubeva, Maria A.,Maximov, Anton L.
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- Tetranuclear ruthenium clusters anchored on polyoxometalates catalyze the hydrogenation of methyl levulinate in water
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Novel ionic materials derived from ruthenium cluster cation and tungstoaluminate anions have been developed and are proved to be robust, efficient and recyclable catalysts toward the selective hydrogenation of methyl levulinate (ML) to gamma-valerolactone (GVL) or methyl 4-hydroxypentanoate (4-HPTM) by tuning the acidity. The structure and properties of the catalysts were characterized using elemental analysis, 1H NMR, 27Al NMR, FT-IR, X-ray diffraction, and pyridine absorbed FT-IR, etc. The catalysts not only afforded excellent conversion and selectivity for GVL (99%) or 4-HPTM (88%) in the aqueous phase under very mild conditions (25 °C) but also showed good recyclability in five consecutive cycles without any significant loss in catalytic activity. In contrast to the direct intramolecular esterification of 4-HPTM in most previous reports, further characterization revealed that intramolecular cyclization proceeded via a metal and counterion (tungstoaluminate)-assisted mechanism on the anchored Ru cluster catalyst; moreover, the strong acidity on the catalysts can hamper the conversion of 4-HPTM into GVL. This rendered the Ru cation complex/tungstoaluminate ionic materials a potential candidate for the efficient production of either GVL or 4-HPTM from ML hydrogenation under very mild conditions. This journal is
- Chen, Manyu,Cui, Kai,Hou, Zhenshan,Peng, Qingpo,Qiao, Wencheng,Wang, Jiajia,Wei, Xinjia,Yao, Yefeng,Zhao, Xiuge
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supporting information
p. 21215 - 21224
(2021/12/04)
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- In Situ Generated Nickel Phosphide Based Catalysts for Hydroprocessing of Levulinic Acid
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Abstract: This article describes the production of unsupported nickel phosphide catalysts generated in situ in а reaction mixture from water-soluble and oil-soluble precursors during the hydroconversion of levulinic acid. These catalysts contain crystalline phases, specifically Ni12P5 and Ni(PO3)2. During the hydrogenation of levulinic acid in toluene in the presence of NiP–TOP, a lower temperature and a shorter reaction time contribute to the formation of γ-valerolactone (100% selectivity). A higher temperature and a longer reaction time favor the formation of valeric acid (94% selectivity). In the hydrogenation of levulinic acid in ethanol in the presence of NiP–H3PO2, the main reaction product is ethyl levulinate (95% selectivity).
- Golubeva
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p. 670 - 675
(2021/03/29)
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- Efficient Conversion of Biomass Derived Levulinic Acid to γ-Valerolactone Using Hydrosilylation
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Converting biomass into value-added chemicals is of significant interest and we report an efficient hydrosilylation to convert levulinic acid to γ-valerolactone using cost-effective silanes such as PMHS and TMDS with B(C6F5)3 as catalyst. This metal free methodology works at room temperature reaching TONs and TOFs up to 16000 and 2000 h?1. Insights into the reaction mechanism are reported.
- Garg, Nitish K.,Schmalz, Veronika,Johnson, Magnus T.,Wendt, Ola F.
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supporting information
p. 5243 - 5247
(2021/10/19)
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- Tuning the selectivity of electrochemical levulinic acid reduction to 4-hydroxyvaleric acid: A monomer for biocompatible and biodegradable plastics
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Levulinic acid (LA) is a biomass-derived feedstock that can be converted to a wide array of value-added products; several of these can be accessed efficiently by electrochemical conversion. Herein, we present a study of factors governing LA conversion in electrochemical environments. Most notably, we identify an unprecedentedly efficient pathway forming 4-hydroxyvaleric acid (HVA), a valuable monomer that can be used for production of bio-polyesters - specifically, poly(hydroxy acids) - as well as γ-valerolactone (GVL) (a green fuel/solvent) and other fine chemicals. This method shows >99.9% selectivity and >80% faradaic efficiency for conversion above 80%. Production rates higher than 40 g L-1 h-1 (or 200 kg L-1 mgeom.-2 h-1) were achieved; these are substantially higher than reports for compatible biochemical methods. We further identify mechanistic insights regarding the steering of selectivity toward this new pathway in comparison to known electrochemical routes toward valeric acid (VA) or to GVL. Finally, we provide a fast, sequential one-pot synthesis route to transform electrochemically-produced HVA to GVL with higher overall selectivity and faradaic efficiency than can be achieved by direct aqueous electrochemical conversion of LA to GVL (96% conversion and >99.9% selectivity, giving a total yield of 93% from LA). This journal is
- Fishler, Yuval,Holewinski, Adam,Lucas, Francisco W. S.
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supporting information
p. 9154 - 9164
(2021/11/27)
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- STRONGLY LEWIS ACIDIC METAL-ORGANIC FRAMEWORKS FOR CONTINUOUS FLOW CATALYSIS
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Lewis acidic metal-organic framework (MOF) materials comprising triflate-coordinated metal nodes are described. The materials can be used as heterogenous catalysts in a wide range of organic group transformations, including Diels-Alder reactions, epoxide-ring opening reactions, Friedel-Crafts acylation reactions and alkene hydroalkoxylation reactions. The MOFs can also be prepared with metallated organic bridging ligands to provide heterogenous catalysts for tandem reactions and/or prepared as composites with support particles for use in columns of continuous flow reactor systems. Methods of preparing and using the MOF materials and their composites are also described.
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Paragraph 0230-0232; 0239; 0258
(2021/02/26)
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- The relevance of Lewis acid sites on the gas phase reaction of levulinic acid into ethyl valerate using CoSBA-xAl bifunctional catalysts
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A series of Co supported on Al-modified SBA-15 catalysts has been studied in the gas phase direct transformation of levulinic acid (LA) into ethyl valerate (EV) using a continuous fixed-bed reactor and ethanol as solvent. It was observed that once the intermediate product gamma-valerolactone (GVL) has been formed, the presence of aluminum is required for the selective transformation to EV. Three Lewis acid sites (LAS) are identified (from highest to lowest acid strength): aluminum ions in tetrahedral and octahedral coordination and Co2+sites. The intrinsic activity of these LAS for the key reaction, the GVL ring opening, decreases with the strength of these acid sites, but so does the undesirable formation of coke, also catalyzed by these centers. The best catalyst was that with the highest Al content, CoSBA-2.5Al, that reached an EV yield of up to 70%. This result is associated with the presence of LAS attributed to the presence of Co2+surface species that, although having low intrinsic activity in the selective GVL ring-opening reaction, are highly concentrated in this sample and also possess less activity in the undesirable and deactivating formation of coke. These Co2+LAS have been stabilized by incorporation of aluminum into the support, modifying the reducibility and dispersion of cobalt species. Additionally, the lower proportion of metallic Co species decreases the hydrogenating capacity of this catalyst. This decrease is a positive result because it prevents GVL hydrogenation to undesired products. This catalyst also showed promising stability in a 140 h on-stream run.
- Cecilia, J. A.,Dumesic, J. A.,Jiménez-Gómez, C. P.,López Granados, M.,Maireles-Torres, P.,Mariscal, R.,Mu?oz-Olasagasti, M.
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p. 4280 - 4293
(2021/06/30)
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- Method for continuously preparing gamma-valerolactone from furfuryl alcohol by one-step method
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The invention discloses a method for integrally and continuously producing gamma-valerolactone from furfuryl alcohol through hydration and hydrogenation, which comprises the steps of by using furfuryl alcohol as a reaction raw material, hydrating furfuryl alcohol into levulinic acid under the action of a solid acid catalyst and a metal catalyst, and then hydrogenating to obtain gamma-valerolactone. According to the method, side reactions such as furfuryl alcohol hydrogenation or polymerization are reduced or avoided through sectional assembly of the catalyst; and meanwhile, gamma-valerolactone is used as a reaction solvent to improve the actual utilization concentration of furfuryl alcohol. The method is mild in reaction condition, separation and purification of the product from the solvent and separation of the catalyst from the product are avoided, the technological process can be effectively shortened, and the operation cost is saved.
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Paragraph 0067-0080
(2021/04/26)
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- Highly efficient selective hydrogenation of levulinic acid to γ-valerolactone over Cu-Re/TiO2bimetallic catalysts
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Highly active and thermally stable Cu-Re bimetallic catalysts supported on TiO2 with 2.0 wt% loading of Cu were prepared via an incipient wetness impregnation method and were applied for liquid phase selective hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) in H2. The effect of the molar ratios of Cu?:?Re on the physico-chemical properties and the catalytic performance of the Cu-Re/TiO2 catalysts was investigated. Moreover, the influence of various reaction parameters on the hydrogenation of LA to GVL was studied. The results showed that the Cu-Re/TiO2 catalyst with a 1?:?1 molar ratio of Cu to Re (Cu-Re(1?:?1)/TiO2) exhibited the highest performance for the reaction. Complete conversion of LA with a 100% yield of GVL was achieved in 1,4-dioxane solvent under the reaction conditions of 180 °C, 4.0 MPa H2 for 4 h, and the catalyst could be reused at least 6 times with only a slight loss of activity. Combined with the characterization results, the high performance of the catalyst was mainly attributed to the well-dispersed Cu-Re nanoparticles with a very fine average size (ca. 0.69 nm) and the co-presence of Cu-Re bimetal and ReOx on the catalyst surface.
- Deng, Shuguang,Liu, Kai,Liu, Yingxin,Ma, Jiao,Wei, Zuojun,Xiao, Shuwen,Zhang, Kaiyue,Zhang, Meihua
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p. 602 - 610
(2022/01/20)
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- Improvement on the catalytic performances of butyl levulinate hydrogenation to γ-valerolactone over self-regenerated CuNiCoB/Palygorskite catalyst
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The acid-activated Palygorskite (H+-PAL) was applied to support Cu(M)NiCoB amorphous alloy catalysts with high-activity and self-regeneration ability for selective hydrogenation of butyl levulinate (BL) to γ-valerolactone (GVL). The catalysts were characterized by ICP-OES, nitrogen physisorption, XRD, FE-SEM, TEM, XPS, H2-TPD, NH3-TPD and FTIR-pyridine adsorption techniques. Compared to the unsupported Cu0.5Ni1Co1B catalyst, the Cu0.5Ni1Co1B/H+-PAL catalyst showed the highest GVL yield of 96.3 % with BL conversion of 99.7 % at 200 °C. When Mo was doped into the Cu0.5Ni1Co1B/H+-PAL catalyst, the GVL yield showed gradually increase to 95.7 % with BL conversion of 100 % after five times run. The high activity and self-regeneration ability was attributed to the Mo doping effect and the synthetic effect between Cu hydrogenation active species and H+-PAL support. Various characterization results indicated that Mo acted as both structural promoter to improve the dispersion of metallic Cu and CuMoNiCoB amorphous alloy and electronic promoter to enhance the formation and increase the fraction of Cu+ species. In addition, the incorporation of Mo provided more Lewis acid sites to promote BL conversion to GVL and GVL conversion to 1,4-PDO and n-PeOH. On the basis of characterization and catalytic performance testing results, the synergistic effect between CuMoNiCoB amorphous alloy and Cu2O/Cu hydrogenation sites and Lewis/Br?nsted acid site of H+-PAL support is considered to be the key to produce GVL.
- Guo, Haijun,Ding, Shuai,Zhang, Hairong,Wang, Can,Peng, Fen,Xiong, Lian,Chen, Xinde,Ouyang, Xinping
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- γ-Valerolactone synthesis from α-angelica lactone and levulinic acid over biobased multifunctional nanohybrid catalysts
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The selective chemical conversion of biomass components to useful bioproducts may contribute to a renewable resource-based economy. The selective production of target bioproducts may be accomplished using heterogeneous catalysts operating under relatively moderate reaction conditions. In this work, carbohydrate biomass derived α-angelica lactone (AnL) and levulinic acid (LA) were converted to the versatile bioproduct γ-valerolactone (GVL), in the presence of nanohybrid catalysts (M-FDCA) and the microcrystalline metal-organic framework CAU-28, all of which were synthesized from bio-based 2,5-furandicarboxylic acid (FDCA) and a metal (M = Zr or Hf) precursor. The nanohybrids were prepared in a simple fast (FT) fashion, and, for comparison, via a conventional solvothermal (S) procedure. The M-FDCA catalysts stood on a higher footing than CAU-28 in the conversion of AnL and LA to GVL. The superior results for the M-FDCA catalysts may be partly due to their higher ratio Sext:SBET and nano-features, which may advantageously enhance active sites accessibility. In particular, the Hf-FDCA catalysts were stable and performed superiorly to the Zr-FDCA ones. Experimental mechanistic studies shed light on the multifunctional behavior of the hybrid catalysts in the one-pot conversion of AnL-to-GVL, which involved acid and reduction chemistry.
- Antunes, Margarida M.,Fernandes, Auguste,Silva, Andreia F.,Valente, Anabela A.
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- Conversion of levulinic acid to γ-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Br?nsted acid sites
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Zr-containing UiO-66 and MOF-808 are evaluated for converting levulinic acid (LA) into γ-valerolactone (GVL) through various routes: (i) Step-wise esterification of LA to n-butyl levulinate (nBuL) and Meerwein-Ponndorf-Verley (MPV) reduction to GVL; (ii) One-pot two-steps esterification with n-butanol followed by MPV reduction with sec-butanol; and (iii) direct conversion of LA into GVL through a tandem reaction. Selection of this multistep complex reaction evidences the participation of the different acid sites (Lewis or Br?nsted) of the material in each individual step: Br?nsted-induced acid sites catalyze esterification reaction efficiently, while Lewis acid sites are the preferred sites for the MPV step. Sulfation of MOF-808 is used to enhance the Br?nsted acidity of MOF-808, which improves the performance for esterification. However, the sulfate groups introduced are detrimental for the MPV step, since they reduce the intra-pore space available to form the required bulky transition state. These results evidence the need to find the best equilibrium between Br?nsted and Lewis acid sites to optimize the outcome of this multistep reaction.
- Cirujano, F. G.,Guarinos, J. M.,Llabrés i Xamena, F. X.,Rapeyko, A.
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- Conversion of glucose to levulinic acid and upgradation to γ-valerolactone on Ru/TiO2catalysts
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Combining glucose dehydration and the subsequent hydrogenation in one pot is a preferable approach for process development as such a method allows in situ generation of the reactive intermediate to undergo further reaction without extra energy-intensive separation. Herein, phosphotungstic acid and various types of titania (anatase, rutile, P25) supported Ru-based catalysts were considered as the dehydration and hydrogenation catalysts, respectively. Modulating the different reactant media (N2, H2), various products were obtained with GBL-H2O as the solvent. A considerable yield (42%) of levulinic acid (LA) and γ-valerolactone (GVL) (40%) were obtained in nitrogen and subsequent hydrogen. Ru/TiO2 (rutile) was the favorable hydrogenation catalyst among the three types of Ru/TiO2. Meanwhile, a certain amount of sorbitol (36%) was obtained in pure hydrogen. The hydrogenation of glucose is more likely to occur than the glucose dehydration. The physicochemical properties of the catalysts were characterized by XRD, BET, TPR, STEM and in situ CO/FT-IR, and the results show that well-dispersed Ru particles are located on the rutile crystallites, which facilitated the hydrogenation of LA. A strong metal support interaction (SMSI) was responsible for the various microstructure properties and the different hydrogenation reactivity. This work allows a better understanding of the reaction paths of glucose conversion.
- Ding, Guoqiang,Liu, Yubo,She, Haohao,Yang, Yong,Zhao, Guoping,Zhu, Yulei
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p. 14406 - 14413
(2021/08/23)
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- Method for synthesizing gamma-valerolactone
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The invention discloses a method for synthesizing gamma-valerolactone. The method comprises the following steps: adding methyl levulinate, CH3OH and an iridium complex catalyst into a reaction container, heating to react for several hours, cooling to room temperature, spin-drying a solvent, and then performing column separation to obtain a target compound. According to the method, methyl levulinate reacts with methanol under the catalytic action of a metal iridium catalyst to synthesize a target product in one step, wherein the raw materials used in the reaction are commercial reagents, the water generated in the reaction is a byproduct, environmental pollution is avoided, methanol is used as a raw material and a solvent in the reaction, and compared with an organic matter used as a solvent in a previous synthesis method, the method is more environment-friendly, and the atom economy of the reaction is high.
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Paragraph 0023-0025
(2021/06/06)
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- A Cationic Ru(II) Complex Intercalated into Zirconium Phosphate Layers Catalyzes Selective Hydrogenation via Heterolytic Hydrogen Activation
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Catalytic hydrogenations constitute economic and clean transformations to produce pharmaceutical and a multitude of fine chemicals in chemical industry. Herein, we report a cationic Ru(II) complex intercalated into zirconium phosphate (ZrP) layers that enables the efficient catalytic conversion of furfural and other biomass-derived carbonyl compounds into the corresponding alcohols through selective hydrogenation of C=O group. The ZrP layers acted not only as a support for the Ru-complex, but also as the new ligands to tune the Ru(II) center via forming Ru?O bond. The resulting catalysts exhibit excellent catalytic performance and can be easily recycled for six times without significant loss of activity and selectivity. The Ru(II) complex-intercalated catalysts have been characterized by XRD, SEM, HRTEM, HAADF-STEM, XPS, FT-IR, DR-UV/Vis, EXAFS and XANES. Especially, it is observed that the appropriate interlayer spacing between ZrP layers is favorable to stabilize the Ru(II) complex. Notably, on the basis of the further characterization and density functional theory (DFT) calculation, it is identified that the interaction of cationic Ru(II) complex and P?OH group within ZrP layers leads to the high catalytic performance in selective hydrogenation, and the newly formed Ru?O?P species plays a crucial role in the heterolytic hydrogen activation and selective hydrogenation of biomass-derived compounds containing a carbonyl group.
- Chen, Manyu,Xia, Jie,Li, Huan,Zhao, Xiuge,Peng, Qingpo,Wang, Jiajia,Gong, Honghui,Dai, Sheng,An, Pengfei,Wang, Haifeng,Hou, Zhenshan
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p. 3801 - 3814
(2021/08/03)
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- Efficient Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Polyoxometalate@Zr-Based Metal-Organic Frameworks: The Synergistic Effect of Bro?nsted and Lewis Acidic Sites
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Catalytic transformation of levulinic acid (LA) to γ-valerolactone (γ-GVL) is an important route for biomass upgradation. Because both Bro?nsted and Lewis acidic sites are required in the cascade reaction, herein we fabricate a series of H3PW12O40@Zr-based metal-organic framework (HPW@MOF-808) by a facile impregnation method. The synthesized HPW@MOF-808 is active for the conversion of LA to γ-GVL using isopropanol as a hydrogen donor. Interestingly, with the increase in the HPW loading amount, the yield of γ-GVL increases first and then decreases, and 14%-HPW@MOF-808 gave the highest γ-GVL yield (86%). The excellent catalytic performance was ascribed to the synergistic effect between the accessible Lewis acidic Zr4+ sites in MOF-808 and Bro?nsted acidic HPW sites. Based on the experimental results, a plausible reaction mechanism was proposed: the Zr4+ sites catalyze the transfer hydrogenation of carbonyl groups and the HPW clusters promote the esterification of LA with isopropanol and lactonization to afford γ-GVL. Moreover, HPW@MOF-808 is resistant to leaching and can be reused for five cycles without significant loss of its catalytic activity.
- Li, Jie,Zhao, Shuaiheng,Li, Zhen,Liu, Dan,Chi, Yingnan,Hu, Changwen
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p. 7785 - 7793
(2021/05/04)
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- One-step upgrading of bio-based furfural to γ-valerolactone: Via HfCl4-mediated bifunctional catalysis
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γ-Valerolactone (GVL) is an attractive biomass-derived platform molecule that plays an important role in the production of biofuels and biopolymers. The synthesis of GVL from renewable biomass and its derivatives has great application prospects but also presents challenges due to the multiple conversion steps involved. Here, a HfCl4-mediated acid-base bifunctional catalytic system was developed, which was demonstrated to be efficient for upgrading furfural (FF) to GVL in a single pot with unprecedented performance. The Lewis acidity of Hf4+ and moderate basicity of HfO(OH)2·xH2O, and strong Br?nsted acidity of HCl in situ generated from HfCl4 hydrolysis were found to play a synergistic role in the cascade reaction processes, mainly contributing to the pronounced catalytic activity. The effects of the key reaction parameters, such as the catalyst dosage, reaction time, and temperature, on GVL production were optimized by response surface methodology. It is worth mentioning that the recovered catalyst after thermal treatment could be directly used for the hydrogen transfer processes, like FF-to-furfuryl alcohol conversion. This catalytic strategy opens a new avenue for the selective conversion of biomass feedstocks involving multiple steps and complex processes.
- Li, Hu,Li, Mingrui,Lin, Xialing,Liu, Yixuan,Tan, Jinyu,Yang, Song
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p. 35415 - 35424
(2021/11/30)
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- Domino transformation of furfural to γ-valerolactone over SAPO-34 zeolite supported zirconium phosphate catalysts with tunable Lewis and Br?nsted acid sites
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The economic and highly efficient synthesis of γ-valerolactone (GVL) is being increasingly focused due to its wide applications in solvent, chemical, and fuel. Herein, a range of SAPO-34 supported zirconium phosphate (ZPS-X) catalysts were prepared for a facile one-pot conversion of furfural (FF) to GVL through a series of cascaded reactions involving transfer hydrogenation, etherification, alcoholysis and esterification. The introduction of zirconium phosphate renders the formation of relatively strong Lewis acid sites, and the amount of Lewis (L) and Br?nsted (B) acid sites of ZPS-X catalysts could be modified by adjusting the molar ratio of Zr to P (Zr/P ratio). Specifically, ZPS-1.0 having an appropriate Zr/P ratio with relatively strong L acid sites exhibited superior activity and selectivity for the production of GVL from FF.
- Li, Weile,Li, Mengzhu,Liu, Huai,Jia, Wenlong,Yu, Xin,Wang, Shuai,Zeng, Xianhai,Sun, Yong,Wei, Junnan,Tang, Xing,Lin, Lu
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- Transfer Hydrogenation of Levulinic Acid to γ-Valerolactone and Pyrrolidones Using a Homogeneous Nickel Catalyst
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We report a well-defined homogeneous nickel-based catalyst using the complex [dippeNi(COD)] (dippe=1,2-bis(diisopropyl phosphino)ethane) as a catalytic precursor with high activity in the hydrogenation of levulinic acid (LVA) to yield γ-valerolactone (GVL) under relatively mild conditions (4 h, 120 °C); formic acid (FA) is the transfer hydrogenation agent in a dehydrogenation-hydrogenation process. Under optimized conditions, GVL was obtained with excellent yield (>99 %) and selectivity (>99 %). The Ni-catalyst was assessed in the LVA hydrogenation with a variety of primary amines using an excess of FA (4 eq) as hydrogen donor at 15 h and 170 °C to produce 2-pyrrolydones with excellent yield (>99 %) and fair to good selectivity (from 68 to 92 %).
- Jurado-Vázquez, Tamara,Arévalo, Alma,García, Juventino J.
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supporting information
p. 445 - 450
(2021/01/18)
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- Catalytic Transfer Hydrogenation of Ethyl Levulinate to γ-Valerolactone Over Ni Supported on Equilibrium Fluid-Catalytic-Cracking Catalysts
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Nickel supported on equilibrium fluid-catalytic-cracking catalysts (Ni/E-cats) were prepared by a simple grinding-pyrolysis method and employed for the transfer hydrogenation of ethyl levulinate (EL) to γ-valerolactone (GVL). 96.2% selectivity of GVL and 90.3% conversion of EL were obtained at 180?°C for 6?h over 30-Ni/E-cat. Through XRD, N2 adsorption–desorption, NH3-TPD and SEM analysis, the high activity of the 30-Ni/E-cat catalyst was attributed to its dispersed Ni metal active centers and available acidic sites. Catalytic probe test revealed that metal and acid sites of Ni/E-cat played a synergistic catalytic role in the synthesis of GVL in 2-propanol, where Ni metal sites contribute to the hydrogenation of ketone group in EL, and acid sites of E-cat promoted the lactonization of intermediate ethyl- or isopropyl 4-hydroxyvalerate. Two reaction pathways and synergistic mechanism were proposed in this catalytic system. Moreover, Ni/E-cat catalyst exhibited good stability up to four cycles without obvious loss of catalytic activity. Graphic Abstract: [Figure not available: see fulltext.]
- Chen, Han,Xu, Qiong,Li, Hui,Liu, Jian,Liu, Xianxiang,Huang, Geng,Yin, Dulin
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p. 538 - 547
(2020/07/30)
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- Mild reduction with silanes and reductive amination of levulinic acid using a simple manganese catalyst
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A manganese-based catalytic system using the commercially available complex [Mn(CO)5Br] was studied for the selective reduction of levulinic acid (LA) to 2-methyl-tetrahydrofuran (MTHF). We further studied the production of pyrrolidines via its reductive amination using silanes (phenylsilane and tetramethyldisiloxane). The results showed high efficiency and selectivity for this reaction leading to high yields using mild reaction conditions.
- Garcia, Juventino J.,Roa, Diego A.
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- Ru Nanoparticles on a Sulfonated Carbon Layer Coated SBA-15 for Catalytic Hydrogenation of Furfural into 1, 4-pentanediol
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Furfural (FFR) is one of the most important biomass-derived chemicals. Its large-scale availability calls for the exploration of new transformation methods for further valorization. Herein, we demonstrate that Ru nanoparticles (Ru NPs)-supported on a sulfonated carbon layer coated SBA-15 can be employed as an efficient bi-functional catalyst for one step conversion of FFR into 1,4-pentanediol (1,4-PeDO). The optimum bi-functional catalyst can afford the full the conversion of FFR and 86% selectivity to 1,4-PeDO. The catalysts have been characterized thoroughly by using a complementary combination of powder X-ray diffraction, N2 adsorption–desorption, scanning/transmission electron microscopy, Fourier transform infrared spectroscopy, elemental analysis, and X-ray photoelectron spectroscopy. The characterization revealed that acidic groups (–SO3H) have been introduced on the surface of the carbon layer coated SBA-15 support after sulfonation with 98% H2SO4 and the surface acidity can be tuned facilely by the sulfonating time. Meantime, Ru(0) sites was highly dispersed via an impregnation and sequential reduction and directly adjacent to the surface –SO3H group. There existed an electronic interaction between Ru(0) sites and sulfonic groups, in which the electronic transfer from sulfonic sites to Ru(0) sites occurred. Br?nsted acid sites (–SO3H) have a significant influence on the FFR conversion and the selectivity to 1,4-PeDO. The ordered mesoporous structure, the appropriate density of acid sites and the electron-rich Ru(0) sites accounted for the the excellent performance of the catalyst for an efficient production of 1,4-PeDO from FFR. Graphic Abstract: [Figure not available: see fulltext.].
- Cui, Kai,Qian, Wei,Shao, Zhengjiang,Zhao, Xiuge,Gong, Honghui,Wei, Xinjia,Wang, Jiajia,Chen, Manyu,Cao, Xiaoming,Hou, Zhenshan
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p. 2513 - 2526
(2021/02/05)
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- Eco-Friendly Natural Clay: Montmorillonite Modified with Nickel or Ruthenium as an Effective Catalyst in Gamma-Valerolactone Synthesis
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Ni/Ru metals supported on cheap and available support montmorillonite K10 were used for the selective hydrogenation of levulinic acid to γ-valerolactone. Different loadings of the metals were applied by the impregnation method, and detailed characterization was performed (UV–VIS, XRD, TPR, TPD, particle size distribution, SEM, XRF). Metals’ homogeneous distribution on the surface was confirmed. The selectivity to the desired product was almost independent on the used material. A detailed study of the influence of solvents on the studied reaction was also performed—protic alcohol-based solvents caused the formation of levulinic and valeric acid esters in the reaction mixture. The selectivity was influenced mainly by the alcohol structure (the highest selectivity obtained using isopropyl alcohol and sec-butanol). Mainly the solvent’s donor number (except ethanol) influenced the reaction rate. The prepared catalysts are promising, available, and cheap materials for the studied reaction. Solvent may significantly influence the yield of γ-valerolactone. Graphic Abstract: [Figure not available: see fulltext.].
- ?erveny, Libor,Trejbal, Ji?í,Vaňková, Michaela,Vrbková, Eva,Vysko?ilová, Eli?ka
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- Flow synthesis of N-alkyl-5-methyl-2-pyrrolidones over Ni2P/SiO2 catalyst
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N-alkyl-5-methyl-2-pyrrolidones are an attractive alternative to the common solvent N-methyl-2-pyrrolidone (NMP) and can be used as starting materials for synthesis of various valuable chemicals. Reductive amination of alkyl levulinates derived from biomass feedstock is a promising method for production of these compounds. In the present work, N-alkyl-5-methyl-2-pyrrolidones were obtained in excellent yields by reductive amination of ethyl levulinate with alkylamines over SiO2-supported nickel phosphide in a flow reactor using molecular hydrogen as a reducing agent. At the same time, aromatic amines and 1-nitropropane give a lower yield of the corresponding pyrrolidones. The influence of the solvent nature, temperature, pressure, hydrogen and liquid flow rates on the catalyst performance was studied.
- Bukhtiyarova, Galina A.,Nuzhdin, Alexey L.,Shamanaev, Ivan V.,Wang, Yazhou
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- Rhodium porphyrin molecule-based catalysts for the hydrogenation of biomass derived levulinic acid to biofuel additive γ-valerolactone
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Rhodium-meso-tetraphenylporphyrin (RhTPP) and rhodium-meso-tetrakis(4-carboxyphenyl)porphyrin (RhTCPP) complexes were synthesized and surface grafted on amine-functional mesoporous molecular sieves. The formation of ligands (TPP and TCPP) and their rhodium complexes (RhTPP and RhTCPP) was evident with the help of 1H NMR, 13C NMR, mass spectral and elemental (CHN) analysis. The absence of the pyrrole proton of the porphyrin units on RhTPP and RhTCPP confirmed the successful formation of metallo-macro-molecules. Further, RhTPP and RhTCPP were fixed on the surface of SBA-15 through amino-silane as the linker. The rhodium containing homogeneous (RhTPP and RhTCPP) and heterogeneous catalysts (RhTPP-SBA-AM and RhTCPP-SBA-AM) were used for biomass-derived levulinic acid hydrogenation. Further, the synthesized catalysts were utilized for the hydrogenation of various organic molecules having arene, carbonyl, and alkene functionality under moderate reaction conditions. Both homogeneous and heterogeneous catalysts showed more than 95% levulinic acid conversion even after four cycles. The homogeneous RhTPP and RhTCPP yielded γ-valerolactone (GVL) as a major product, whereas heterogeneous catalysts showed only comparable γ-valerolactone (GVL) selectivity, with improved reusability and recylability in the presence of relatively lower amounts of rhodium complexes. Among RhTPP and RhTCPP, RhTPP showed better selectivity for γ-valerolactone (GVL) compared to RhTCPP. Further, as the number of catalytic runs increased, there was a gradual increase in diol selectivity, which was predominant in the case of RhTCPP, possibly due to the presence of the hydrophilic carboxylate ion which facilitates the interaction of water by-products with γ-valerolactone and favours diol formation. The hydrophobic environment of the RhTPP catalyst facilitated the formation of γ-valerolactone as the major product even in the fifth run. This journal is
- Anjali, Kaiprathu,Christopher, Jayaraj,Sakthivel, Ayyamperumal,Venkatesha, Naragalu J.
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supporting information
p. 11064 - 11075
(2020/07/15)
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- Production of γ-Valerolactone from One-Pot Transformation of Biomass-Derived Carbohydrates Over Chitosan-Supported Ruthenium Catalyst Combined with Zeolite ZSM-5
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It remains as a challenge to directly transform the biomass-derived C5 carbohydrates, such as furfural (FF) and its upstream product xylose and hemicellulose, to γ-valerolactone (GVL), a versatile renewable chemical platform, due to various restrictions in the current synthetic strategies. Using formic acid as green hydrogen source, we synthesized the recyclable chitosan-Ru/PPh3 catalyst system, effective for both the hydrogenation of FF to furfuryl alcohol (FAL) and the reduction of levulinic acid (LA) or ethyl levulinate (EL) to GVL, affording up to 99 % product yields. The combination of chitosan-Ru/PPh3 with ZSM-5 could successfully achieve up to 79 % yield of GVL from one-pot conversion of FF under mild condition. Preliminary studies indicated that this method could also be applied to the direct conversion of biomass-derived C5 carbohydrates such as xylose and hemicellulose to GVL in 37 % or 30 % yield, respectively.
- Wang, Tianlong,He, Jianghua,Zhang, Yuetao
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p. 1611 - 1619
(2020/03/04)
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- Photoredox-Catalyzed α-C(sp3)-H Activation of Unprotected Secondary Amines: Facile Access to 1,4-Dicarbonyl Compounds
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A photoredox-catalyzed α-C(sp3)-H activation approach of unprotected secondary amines is reported. Such transformations provide facile access to various 1,4-dicarbonyl compounds using readily available amines and α,β-unsaturated compounds as feedstocks under air conditions. The substrate scope of this method is broad, and a wide array of functional groups are tolerated.
- Zhang, Qian,Huang, Yan,Zhan, Le-Wu,Tang, Wan-Ying,Hou, Jing,Li, Bin-Dong
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supporting information
p. 7460 - 7464
(2020/10/09)
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- Preparation methods of gamma-valerolactone and levulinate compounds
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The invention discloses preparation methods of a gamma-valerolactone and levulinate compounds. The preparation method of the gamma-valerolactone comprises reacting furfural and secondary alcohol underthe action of a catalyst to prepare gamma-valerolactone, wherein the catalyst is M(R)n, M is selected from Ce, Sc, Y, Yb or Lu, and R is selected from trifluoromethanesulfonic acid group, perfluorobutanesulfonic acid group, heptadecafluorooctane sulfonic acid group, di(trifluoromethanesulfonyl)amido or di(perfluorobutanesulfonyl) amido. According to the invention, commercial single Lewis acid isused as a catalyst; step-by-step operation and a complex product separation process in a traditional gamma-valerolactone preparation process are avoided, the method is simple and efficient, low-cost production of gamma-valerolactone is realized, and particularly, one-step conversion of biomass (such as xylose, xylan and corncobs) into gamma-valerolactone can be realized by utilizing a commercial single catalyst.
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Paragraph 0162-0172
(2020/07/29)
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- Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol under Mild Conditions over Zr-MOFs: Exploring the Role of Metal Node Coordination and Modification
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The catalytic transfer hydrogenation (CTH) reaction is considered as a potential route for upgrading bio-based carbonyls to their corresponding alcohols. Herein, a series of Zr-based metal-organic frameworks (Zr-MOFs) containing various types of metal node to ligand coordinations were synthesized and tested for CTH of furfural (FUR) to furfuryl alcohol (FOL). It was found that metal node coordination plays a more important role than porosity in Zr-MOFs. MOF-808 (synthesized using a scaled-up approach to achieve a higher batch yield), with the lowest metal node to ligand coordination (coordination number 6), was found to be the most active catalyst among the various tested Zr-MOFs. Furthermore, M-MOF-808, modified by simple methanol activation (M), outperformed the pristine MOF-808 in CTH of FUR to FOL even at 30 °C in the presence of 2-propanol (IPA) as the hydrogen source. The simple modification of the metal node in the Zr-MOF changed the acid-base properties of the MOF-808 surface through the development of coordinatively unsaturated sites (CUS), hydroxyl and methoxy groups in the framework of the Zr-MOF, which probably help to facilitate the adsorption of FUR and IPA onto the metal node surfaces of the catalyst. To evaluate the versatility of methanol activation in CTH, further substrates, including other types of biomass and representative carbonyl compounds over M-MOF-808, were tested. To demonstrate heterogeneous catalysis, the catalyst was recycled for five consecutive cycles, with little loss after the first cycle, and was fully characterized to observe any changes in its structure. Mechanistic insights were provided by isotopically labeled 2-propanol-d8 experiments, indicating FUR reduction through transfer hydrogenation. Finally, the reaction mechanism for CTH of FUR to FOL was proposed in detail using density functional theory (DFT) calculations over metal node modified model systems of a 6-connected Zr-MOF.
- Cha, Ga-Young,Chang, Jong-San,Hong, Do-Young,Hwang, Young Kyu,Jung, Jaehoon,Kwak, Jaesung,Kwon, Young-Uk,Lee, Minhui,Oh, Kyung-Ryul,Valekar, Anil H.,Yoon, Ji Woong
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p. 3720 - 3732
(2020/04/15)
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- Solvent-free hydrogenation of levulinic acid to γ-valerolactone using a Shvo catalyst precursor: Optimization, thermodynamic insights, and life cycle assessment
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The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) using the η4-(2,3,4,5-tetraphenylcyclopentadienone) ruthenium tricarbonyl precursor of the well-known Shvo catalyst and H2 pressure was established under solvent-free conditions to achieve 100% conversion and 100% selectivity within 5 hours. Kinetic reaction curves were measured in order to deduce the optimal reaction conditions, which were further evaluated by means of density functional theory (DFT) calculations, and compared with catalytic concepts that consume formic acid or isopropyl alcohol as hydrogen donor. Ultimately, this alternative reaction procedure was subjected to a life cycle assessment (LCA) in comparison with the transfer hydrogenation methodologies, in order to verify its contribution towards a practice of environmentally benign chemistry.
- Bernaerts, Katrien V.,De Wildeman, Stefaan M. A.,Delgove, Marie A. F.,Morick, Lukas,Stouten, Jules,Van Der Meer, Yvonne,Van Slagmaat, Christian A. M. R.
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supporting information
p. 2443 - 2458
(2020/05/13)
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- A tannin-derived zirconium-containing porous hybrid for efficient Meerwein-Ponndorf-Verley reduction under mild conditions
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Both the use of renewable natural sources to prepare catalytic materials and the Meerwein-Ponndorf-Verley (MPV) reduction for carbonyl compounds are very attractive topics in catalysis. In this study, tannins were simply assembled with zirconium in water for the scalable preparation of a heterogeneous zirconium-tannin hybrid catalyst (Zr-tannin). Various characterizations demonstrated the formation of robust porous inorganic-organic frameworks and strong Lewis acid-base sites in Zr-tannin. The cooperative effect of these acid-base sites and the abundant porosity endowed Zr-tannin with a remarkable catalytic performance for the MPV reduction of a broad range of carbonyl compounds to alcohols with 2-propanol under mild conditions. Moreover, Zr-tannin exhibited good recyclability for at least five reaction cycles. This novel strategy using tannins as the raw materials to construct heterogeneous catalytic materials may have a huge potential for green chemical synthesis due to low cost, nontoxicity, and sustainability.
- Leng, Yan,Shi, Langchen,Du, Shengyu,Jiang, Jiusheng,Jiang, Pingping
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p. 180 - 186
(2020/01/13)
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- CNN pincer ruthenium complexes for efficient transfer hydrogenation of biomass-derived carbonyl compounds
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The ligand HCNNOMe (6-(4-methoxyphenyl)-2-aminomethylpyridine) is easily prepared from the commercially available 6-(4-methoxyphenyl)pyridine-2-carbaldehyde by the reaction of hydroxylamine and hydrogenation (H2, 1 atm) with Pd/C. The pincer complexes cis-[RuCl(CNNOMe)(PPh3)2] (1) and [RuCl(CNNOMe)(PP)] (PP = dppb, 2; and dppf, 3) are synthesized from [RuCl2(PPh3)3], HCNNOMe and PP (for 2 and 3) in 2-propanol with NEt3 at reflux and are isolated in 85-93% yield. Carbonylation of 1 (CO, 1 atm) gives [RuCl(CNNOMe)(CO)(PPh3)] (4) (79% yield) which cleanly reacts with Na[BArf4] and PCy3, affording the cationic trans-[Ru(CNNOMe)(CO)(PCy3)(PPh3)][BArf4] (5) (92% yield). These robust pincer complexes display remarkably high catalytic activity in the transfer hydrogenation (TH) of lignocellulosic biomass carbonyl compounds, using 2-propanol at reflux in a basic medium (NaOiPr or K2CO3). Thus, furfural, 5-(hydroxymethyl)furfural and Cyrene are reduced to the corresponding alcohols with 2 and 3, at S/C in the range of 10 000-100 000, within minutes or hours (TOF up to 1 500 000 h-1). The monocarbonyl complex 5 was found to be extremely active in the TH of cinnamaldehyde, vanillin derivatives and ethyl levulinate at S/C in the range of 10 000-50 000. Vanillyl alcohol is also obtained by the TH of vanillin with 5 (S/C = 500) in 2-propanol in the presence of K2CO3.
- Figliolia, Rosario,Cavigli, Paolo,Comuzzi, Clara,Del Zotto, Alessandro,Lovison, Denise,Strazzolini, Paolo,Susmel, Sabina,Zuccaccia, Daniele,Ballico, Maurizio,Baratta, Walter
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supporting information
p. 453 - 465
(2020/01/21)
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