1122-89-0Relevant academic research and scientific papers
Interface synergy between IrOx and H-ZSM-5 in selective C–O hydrogenolysis of glycerol toward 1,3-propanediol
Wan, Xiaoyue,Zhang, Qi,Zhu, Mingming,Zhao, Yi,Liu, Yongmei,Zhou, Chunmei,Yang, Yanhui,Cao, Yong
, p. 339 - 350 (2019)
Site-selective deoxygenation of hydroxyl groups represents essential processes to access valuable functionalized bio-based compounds with industrial potential. One of the challenging tasks in this context is to convert biodiesel-derived glycerol in the presence of abundant water directly to 1,3-propanediol (1,3-PDO), a key component of the emerging polymer industry. Herein, a monometallic iridium supported on H-ZSM-5 in the absence of Re oxophilic metal oxides was prepared via grinding-assisted impregnation procedures and attempted as an effective and recyclable catalyst for the aqueous-phase selective hydrogenolysis of glycerol toward 1,3-PDO in the absence of acid additives. The results revealed the necessity to control the Ir domain dispersions, Ir0/Ir3+ ratio and the amounts of overall acid/Br?nsted acid sites. Activity depended linearly on the amount of overall and Br?nsted acid sites, and 1,3-PDO selectivity increased in the presence of Ir-induced Br?nsted acid sites, denoted as Ir-O(H)-H-ZSM-5. We speculate that Ir-O(H)-H-ZSM-5 are generated by the interfacial synergistic interaction between IrOx and H-ZSM-5 through hydrogen spillover and reverse hydrogen spillover according to the reported literatures. The reaction mechanism to elucidate the role of Ir-O(H)-H-ZSM-5 sites in glycerol hydrogenolysis was also postulated based on extensive characterization and catalytic reaction results.
Process condition-based tuneable selective catalysis of hydroxymethylfurfural (HMF) hydrogenation reactions to aromatic, saturated cyclic and linear poly-functional alcohols over Ni-Ce/Al2O3
Grilc, M.,Likozar, B.,Pomeroy, Brett
supporting information, p. 7996 - 8002 (2021/11/01)
The related immense versatility of a ceria-promoted transition metal catalyst, utilized for the hydrogenation of 5-hydroxymethylfurfural (HMF), is demonstrated in this research study. We reveal a strategy to achieve considerable selective yields of three important high-value HMF-derived compounds by simply modifying the analysed reaction conditions and/or water-containing process medium.
Formic Acid-Assisted Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N-Doped Mesoporous Carbon
Hu, Bin,Warczinski, Lisa,Li, Xiaoyu,Lu, Mohong,Bitzer, Johannes,Heidelmann, Markus,Eckhard, Till,Fu, Qi,Schulwitz, Jonas,Merko, Mariia,Li, Mingshi,Kleist, Wolfgang,H?ttig, Christof,Muhler, Martin,Peng, Baoxiang
supporting information, p. 6807 - 6815 (2021/02/01)
Biomass-derived 5-hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5-dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N-containing and N-free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR-IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C-OH group, lowering the activation barrier of the C?O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd2+ species interacting with pyridine-like N atoms significantly enhance the selective hydrogenolysis of the C?OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H?.
Highly selective ring rearrangement of 5-hydroxymethylfurfural to 3-hydroxymethylcyclopentanon catalyzed by non-noble Ni-Fe/Al2O3
Li, Jiachen,Feng, Yunchao,Wang, Huiqiang,Tang, Xing,Sun, Yong,Zeng, Xianhai,Lin, Lu
, (2021/03/14)
3-Hydroxymethylcyclopentanone (HCPN) has been regarded as a considerable intermediate for the synthesis of polymers, pesticides and fragrances, which is mainly produced from petrochemical refinery. In recent years, the preparation of HCPN from biomass has gradually attracted attention. HCPN can be obtained through the selective ring rearrangement of biomass-based 5-hydroxymethyl furfural (5-HMF). In this paper, the Ni-Fe/Al2O3 was fabricated and used as an efficient catalyst for the production of HCPN, giving a 5-HMF complete conversion with a high HCPN selectivity (86 %) at 160 °C under 4 MPa H2 for 4 h. The optimized Ni-Fe/Al2O3 showed excellent activity towards the production of HCPN compared with monometallic catalysts, suggesting that there was a synergistic effect in Ni-Fe alloy. The introduction of Fe into Ni/Al2O3 improved the H2 adsorption capacity and also changed the acidic/basic sites, which are beneficial for the formation of HCPN. Moreover, Ni-Fe/Al2O3 exhibited superb stability and could be successively used four times without obvious loss in catalytic activity.
Preparation method 2 and 5 - tetrahydrofuran dimethanol
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Paragraph 0072-0106, (2021/11/19)
The preparation method of 2-5 - tetrahydrofuran dimethanol (THFDM) comprises the following steps: mixing a solvent containing 5 - hydroxymethylfurfural raw material with a catalyst, and reacting in an atmosphere containing hydrogen to obtain the 2 and 5 - tetrahydrofuran dimethanol. The purity of 5 - hydroxymethyl furfural raw material is 90 - 99%. The catalyst comprises a carrier and an active component. The active component is loaded on the carrier. The active component includes a noble metal element. The carrier comprises a carbon material. The method is simple in synthesis process, and has a great application prospect in the field of a plurality of fields, especially degradable materials.
Selective aqueous-phase hydrogenation of furfural to cyclopentanol over Ni-based catalysts prepared from Ni-MOF composite
Chen, Changzhou,Jiang, Jianchun,Li, Jing,Ren, Jurong,Wu, Dichao,Xia, Haihong,Zhou, Minghao
, (2021/10/01)
Metal-organic frameworks (MOFs) as an emerging class of porous materials exhibit some unique advantages, including controllable composition, a large surface area, high porosity, and so on. In this work, the spherical NiMo bimetal catalysts supported on porous carbon matrix were prepared using a simple wet impregnation method and studied for selective hydrogenation of furfural (FFA). Three different catalysts were investigated including Ni/C-Mo-BTC, Ni/C-Mo-DHTA and Ni/C-Mo-PTA. Of the catalysts studied the Ni/C-Mo-BTC catalyst could achieve the highest selectivity of CPL (up to 90%) under moderate reaction conditions (140 °C, 2 MPa, 2 h) in aqueous medium. In addition, other Ni-based catalysts (Ni/C-Fe, Ni/C-Zn, Ni/C-Cu, Ni/C-Ce) were also investigated to achieve yields of 20–70% under the same reaction conditions. The influence of temperature, H2 pressure, time and solvent were investigated for the best performing catalyst. Based on the optimal reaction condition, various of furfural derivatives could also be effectively transferred to produce corresponding products. The detailed physicochemical characterization was carried out by means of XRD, SEM, TEM, XPS, NH3-TPD and Raman analysis. In the end, the optimal Ni/C-Mo0.4 catalyst could be recycled magnetically and efficiently applied in the next run for five consecutive recycling tests in the FFA hydrogenation to CPL. The results suggested Ni/C-Mo0.4 catalyst occurred to increasingly favor the formation of Ni-Mo alloys and suggested a metallic active site in FFA hydrogenation with the addition of element Mo. Mechanism study indicated that water was a key factor contributing to the formation of different desired products, which was responsible for the arrangement of furan compound.
Metal-free photocatalytic aerobic oxidation of biomass-based furfural derivatives to prepare γ-butyrolactone
Zhu, Rui,Zhou, Gongyu,Teng, Jia-Nan,Liang, Wanying,Li, Xinglong,Fu, Yao
supporting information, p. 1758 - 1765 (2021/03/09)
Efficient catalytic oxidative C-C bond cleavage with dioxygen is useful and challenging to prepare oxygenated fine chemicals from biomass. Herein, we report a catalytic strategy for the preparation of γ-butyrolactone (GBL) by photocatalytic oxidation of tetrahydrofurfuryl alcohol (THFA), tetrahydrofurfuric acid (THFCA), or other furfural derivatives at room temperature under visible-light irradiation. Metal-free mesoporous graphitic carbon nitride was used as the photocatalyst and O2was used as the oxidant. The effects of various semiconductor catalysts, light sources with different wavelengths, and the reaction time on the photocatalytic oxidation of THFA to GBL were separately investigated. Furthermore, the reaction mechanism was investigated through serious control experiments and the reaction pathway was investigated through density functional theory (DFT) calculations.
Highly Controllable Hydrogenative Ring Rearrangement and Complete Hydrogenation Of Biobased Furfurals over Pd/La2B2O7 (B=Ti, Zr, Ce)
Tong, Zhikun,Gao, Rui,Li, Xiang,Guo, Lingyun,Wang, Jun,Zeng, Zheling,Deng, Qiang,Deng, Shuguang
, p. 4549 - 4556 (2021/09/09)
Developing a highly selective catalyst to upgrade furfurals (5-hydroxymethyl furfural and furfural) to cyclopentanones (3-hydroxymethyl cyclopentanone and cyclopentanone) and tetrahydrofuran alcohols (2,5-bishydroxymethyl tetrahydrofuran and tetrahydrofuran alcohol) is highly significant for biobased fine chemical synthesis. Here, a series of La2B2O7 (B=Ti, Zr, Ce) metal oxides, featuring the same chemical formula but different topological structures are fabricated. After Pd loading, the Lewis acidity and metal-support interaction are well governed by the support type, which further affects the hydrogenation and acid-catalyzed ability. A greater than 82 % yield of cyclopentanones is obtained via a hydrogenative ring rearrangement route over Pd/La2Ti2O7. However, Pd/La2Ce2O7 shows high catalytic efficiency for tetrahydrofuran alcohols with an approximately 80 % yield via a complete hydrogenation route. Additionally, the catalyst exhibits outstanding recycling performance and structural stability. This study presents an interesting design strategy for the selective preparation of cyclopentanones and tetrahydrofuran alcohols through the regulation of the adsorption mechanism.
Selective hydrogenation of 5-hydroxymethylfurfural and its acetal with 1,3-propanediol to 2,5-bis(hydroxymethyl)furan using supported rhenium-promoted nickel catalysts in water
Wiesfeld, Jan J.,Kim, Minjune,Nakajima, Kiyotaka,Hensen, Emiel J. M.
, p. 1229 - 1238 (2020/03/11)
The high reactivity of the formyl group of 5-hydroxymethylfurfural (5-HMF) is problematic, because it leads to undesired oligomerization reactions. This is usually countered by working in dilute non-aqueous solutions. Here, we present a novel approach to convert concentrated aqueous solutions of 5-HMF to 2,5-bishydroxymethylfuran (BHMF), which is a prospective monomer for polyesters and self-healing polymers. Our approach is based on the protection of the formyl group of 5-HMF using acetalization with 1,3-propanediol. Hydrogenation is carried out using an optimized bimetallic Ni-Re catalyst supported on TiO2 at a carefully controlled pH, resulting in balanced rates of deprotection and hydrogenation and high BHMF yield. Under optimized conditions at a benign temperature of 40 °C, hydrogenation of concentrated solutions (10-20 wt%) of protected 5-HMF in water gave 81-89% yields of BHMF without having to resort to platinum-group metals such as palladium or platinum.
Selective hydrogenation of aromatic furfurals into aliphatic tetrahydrofurfural derivatives
Chen, Bingfeng,Han, Buxing,Li, Shaopeng,Liu, Huizhen,Shen, Xiaojun,Wang, Yanyan,Yang, Youdi
supporting information, p. 4937 - 4942 (2020/11/07)
Tetrahydrofurfural (THFF) and 5-hydroxymethyltetrahydro-2-furaldehyde (5-HMTHFF) are important chemicals. Synthesis of THFF and 5-HMTHFF from the selective hydrogenation of furfural (FF) and 5-hydroxymethylfurfural (HMF) is highly desirable. However, it is a great challenge to hydrogenate furanyl rings while keeping CO intact. Herein, we found that Pd/LDH-MgAl-NO3 could efficiently catalyze the hydrogenation of FF to THFF and HMF to 5-HMTHFF in water. At near complete conversion of FF and HMF, the selectivities of THFF and 5-HMTHFF could reach 92.6% and 83.7%, respectively. A series of control experiments showed that both the LDH-MgAl-NO3 support and water solvent played an important role in the unusual performance of the catalytic system. The hydrogenation of the furanyl ring occurred on the surface of Pd. Water prohibited the hydrogenation of the CO group, and the special nature of LDH-MgAl-NO3 prevented hydrogenation of the CO group on the support by the hydrogen spillover. Thus, the furanyl ring was selectively hydrogenated, and high selectivity of the desired product was successfully achieved. As far as we know, efficient hydrogenation of FF to THFF or HMF to 5-HMTHFF has not been reported. This work opens the way to selectively hydrogenate the furanyl ring while keeping CO in the same molecule unchanged. This journal is
