97-99-4Relevant academic research and scientific papers
Supported Ultrafine NiCo Bimetallic Alloy Nanoparticles Derived from Bimetal-Organic Frameworks: A Highly Active Catalyst for Furfuryl Alcohol Hydrogenation
Wang, Huanjun,Li, Xiaodan,Lan, Xiaocheng,Wang, Tiefeng
, p. 2121 - 2128 (2018)
Highly dispersed NiCo bimetallic alloy nanoparticles have been successfully immobilized on the SiO2 frameworks by using heteronuclear metal-organic frameworks (MOFs) as metal alloy precursors. Catalyst characterizations revealed that the average size of NiCo alloy particles was less than 1 nm, with a total metal loading of about 20 wt %. As compared to individual Ni or Co MOF-derived catalysts and the catalysts prepared by the conventional impregnation method, the ultrafine NiCo/SiO2-MOF catalyst showed a much better catalytic performance in the catalytic hydrogenation of furfuryl alcohol (FA) to tetrahydrofurfuryl alcohol (THFA) under mild conditions, giving 99.8% conversion of FA and 99.1% selectivity to THFA. It was found that a significant synergistic effect existed between Co and Ni within the subnanometer NiCo/SiO2-MOF catalyst, which was 2 and 20 times more active than Ni/SiO2-MOF and Co/SiO2-MOF, respectively.
Primary Anion-π Catalysis and Autocatalysis
Zhang, Xiang,Hao, Xiaoyu,Liu, Le,Pham, Anh-Tuan,López-Andarias, Javier,Frontera, Antonio,Sakai, Naomi,Matile, Stefan
, p. 17867 - 17871 (2018)
Epoxide-opening ether cyclizations are shown to occur on π-acidic aromatic surfaces without the need of additional activating groups and with autocatalytic amplification. Increasing activity with the intrinsic π acidity of benzenes, naphthalenediimides (NDIs) and perylenediimides (PDIs) support that anion-π interactions account for function. Rate enhancements maximize at 270 for anion-π catalysis on fullerenes and at 5100 M-1 for autocatalysis. The occurrence of anion-π autocatalysis is confirmed with increasing initial rates in the presence of additional product. Computational studies on autocatalysis reveal transition state and product forming a hydrogen-bonded noncovalent macrocycle, like holding their hands and dancing on the active π surface, with epoxide opening and nucleophile being activated by anion-π interactions and hydrogen bonds to the product, respectively.
A facile conversion of furfural to novel tetrahydrofurfuryl hemiacetals
Dobro?ka, Edmund,Fulajtárová, Katarína,Horváth, Bla?ej,Hronec, Milan,Liptaj, Tibor
, (2020)
An entirely new and highly selective method for preparation of novel tetrahydrofurfuryl hemiacetals is described. The process is based on the catalytic hydrogenation of furfural in an alcohol under mild reaction conditions and at very short reaction times. As a highly active and selective catalyst palladium supported on calcium carbonate is used. Basic sites of the catalyst support enhance the formation of furfuryl hemiacetal as the intermediate which is instantaneously hydrogenated into stable tetrahydrofurfuryl hemiacetal. About 85–90 % yields of tetrahydrofurfuryl hemialkylacetals can be achieved within 20 min by reaction of furfural in alcoholic solutions at 60 °C and 0.3 MPa of hydrogen. The mechanism of reductive acetalization of furfural into tetrahydrofurfuryl hemialkylacetals is proposed.
Highly selective low-temperature hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol catalysed by hectorite-supported ruthenium nanoparticles
Khan, Farooq-Ahmad,Vallat, Armelle,Suess-Fink, Georg
, p. 1428 - 1431 (2011)
Metallic ruthenium nanoparticles intercalated in hectorite (particle size ～ 4 nm) were found to catalyse the hydrogenation of furfuryl acohol to give tetrahydrofurfuryl alcohol in methanolic solution under mild conditions. The best results were obtained at 40 °C under a hydrogen pressure of 20 bar (conversion 100%, selectivity > 99%). After a total turnover number of 1423, the hectorite supported ruthenium nanoparticles are deactivated but can be recycled and regenerated.
Metal-organic-framework derived Co-Pd bond is preferred over Fe-Pd for reductive upgrading of furfural to tetrahydrofurfuryl alcohol
Pendem, Saikiran,Bolla, Srinivasa Rao,Morgan, David J.,Shinde, Digambar B.,Lai, Zhiping,Nakka, Lingaiah,Mondal, John
, p. 8791 - 8802 (2019)
Combined noble-transition metal catalysts have been used to produce a wide range of important non-petroleum-based chemicals from biomass-derived furfural (as a platform molecule) and have garnered colossal research interest due to the urgent demand for sustainable and clean fuels. Herein, we report the palladium-modified metal-organic-framework (MOF) assisted preparation of PdCo3O4 and PdFe3O4 nanoparticles encapsulated in a graphitic N-doped carbon (NC) matrix via facile in situ thermolysis. This provides a change in selectivity with superior catalytic activity for the reductive upgrading of biomass-derived furfural (FA). Under the optimized reaction conditions, the newly designed PdCo3O4@NC catalyst exhibited highly efficient catalytic performance in the hydrogenation of furfural, providing 100% furfural conversion with 95% yield of tetrahydrofurfuryl alcohol (THFAL). In contrast, the as-synthesized Pd-Fe3O4@NC afforded a THFAL yield of 70% after an 8 h reaction with four consecutive recycling tests. Based on different characterization data (XPS, H2-TPR) for nanohybrids, we can conclude that the presence of PdCo-Nx active sites, and the multiple synergistic effects between Co3O4 and Pd(ii), Co3O4 and Pd0, as well as the presence of N in the carbonaceous matrix, are responsible for the superior catalytic activity and improved catalyst stability. Our strategy provides a facile design and synthesis process for a noble-transition metal alloy as a superior biomass refining, robust catalyst via noble metal modified MOFs as precursors.
Highly selective hydrogenation of furfural and levulinic acid over Ni0.09Zn/NC600 derived from ZIFW-8
Li, Zhi-Xin,Wei, Xian-Yong,Liu, Guang-Hui,Meng, Xing-Long,Yang, Zheng,Niu, Shuo,Zhang, Di,Gao, Hua-Shuai,Ma, Zhi-Hao,Zong, Zhi-Min
, (2020)
Highly selective hydrogenation of furfural and levulinic acid (LA) was studied over Ni0.09Zn/NC600 derived from zeolitic imidazolate frameworks. The existence of active Ni3ZnC0.7 particles in Ni0.09Zn/NC600 was confirmed by multiple characterizations. As a result, over Ni0.09Zn/NC600, 99.7% of furfural conversion (FC) and 100% of furan-2-ylmethanol selectivity (FMS) were achieved in isopropanol (IP) at 170 °C for 2 h, while FC and (tetrahydrofuran-2-yl)methanol (THFM) selectivity are 97.5% and 86.4% in water at 150 °C for 1 h. Over the same catalyst, LA was completely converted to γ-valerolactone in water at 95 °C for 0.5 h. The catalyst is still highly active after 6 cycles of recycling with 92.8% of FC and 100% of FMS in IP at 170 °C for 1.5 h and 90.1% of LA conversion and 100% of γ-valerolactone selectivity in water at 80 °C for 0.5 h.
A novel Ru-polyethersulfone (PES) catalytic membrane for highly efficient and selective hydrogenation of furfural to furfuryl alcohol
Bagnato,Figoli,Ursino,Galiano,Sanna
, p. 4955 - 4965 (2018)
A novel catalytic membrane has been synthesised, characterised and evaluated for the selective hydrogenation of furfural to furfuryl alcohol. Unlike conventional methods, involving high pressure and high H2:feed ratios, this work proposes an innovative ruthenium based Catalytic Membrane Reactor (CMR) to overcome mass transfer limitations, resulting in low H2 requirements, high catalytic activity and high selectivity towards furfuryl alcohol. A UV-curable hydrophilic anionic monomer acrylic acid was used as a coating material on a commercial PES membrane and subsequently Ru nanoparticles were added. The hydrogenation of furfural was carried out in a customised catalytic membrane reactor under mild conditions: 70 °C and 7 bar, exhibiting high catalytic activity towards furfuryl alcohol (selectivity >99%) with turnover frequency (TOF) as high as 48000 h-1, 2 orders of magnitude higher than those obtained so far.
High-Temperature Synthesis of Carbon-Supported Bimetallic Nanocluster Catalysts by Enlarging the Interparticle Distance
Zuo, Lu-Jie,Xu, Shi-Long,Wang, Ao,Yin, Peng,Zhao, Shuai,Liang, Hai-Wei
supporting information, p. 2719 - 2723 (2022/02/16)
Supported bimetallic nanoparticle catalysts with small size have attracted wide research attention in catalysis but are difficult to synthesize because high-temperature annealing required for alloying inevitably accelerates metal sintering and leads to larger particles. Here, we report a simple and scalable critical interparticle distance method for the synthesis of a family of bimetallic nanocluster catalysts with an average particle size of only 1.5 nm by using large-surface-area carbon black supports at high temperatures, which consist of 12 diverse combinations of 3 noble metals (Pt, Ru, and Rh) and 4 other metals (Cr, Fe, Zr, and Sn). In this strategy, high-temperature treatments ensure the formation of alloyed bimetallic nanoparticles and enlargement of the interparticle distance on high-surface-area supports significantly suppresses metal sintering. The prepared ultrafine Pt2Sn and RuSn nanocluster catalysts exhibited enhanced performance in catalyzing the synthesis of aromatic secondary amines and the selective hydrogenation of furfural, respectively.
Effect of Ni Metal Content on Emulsifying Properties of Ni/CNTox Catalysts for Catalytic Conversion of Furfural in Pickering Emulsions
Herrera,Pinto-Neira,Fuentealba,Sepúlveda,Rosenkranz,García-Fierro,González,Escalona
, p. 682 - 694 (2020/12/01)
Ni/CNTox catalysts with variable metal content have been prepared to investigate their emulsifying and catalytic properties for the liquid-phase conversion of furfural. The solid catalysts and emulsions were analyzed by several characterization techniques. The catalytic activity linearly increased with increasing Ni content (up to 10 wt.%) before dropping down again for a Ni content of 15 wt.%. The loss of catalytic activity was attributed to larger emulsion droplets formed by the inhibition of hydrophilic sites. All Ni/CNTox catalysts were highly selective to cyclopentanone as a main product, while several changes regarding secondary products were observed. Ni/CNTox catalysts with a Ni content up to 10 wt.% favor the formation of levulinic acid, while catalysts with a Ni content of 15 wt.% were selective to tetrahydrofurfuryl alcohol. This was attributed to an inhibition of the acid sites thus favoring the catalyst's hydrogenation capacity.
Hydrogenative ring-rearrangement of furfural to cyclopentanone over pd/uio-66-no2 with tunable missing-linker defects
Leus, Karen,Liu, Ying-Ya,Shi, Chuan,Sun, Zhichao,Van Der Voort, Pascal,Wang, Anjie,Wang, Chunhua,Wang, Yao,Yang, Yuhao,Yu, Zhiquan
, (2021/09/28)
Upgrading furfural (FAL) to cyclopentanone (CPO) is of great importance for the synthesis of high-value chemicals and biomass utilization. The hydrogenative ring-rearrangement of FAL is catalyzed by metal-acid bifunctional catalysts. The Lewis acidity is a key factor in promoting the rearrangement of furan rings and achieving a high selectivity to CPO. In this work, highly dispersed Pd nanoparticles were successfully encapsulated into the cavities of a Zr based MOF, UiO-66-NO2, by impregnation using a double-solvent method (DSM) followed by H2 reduction. The obtained Pd/UiO-66-NO2 catalyst showed a significantly better catalytic performance in the aforementioned reaction than the Pd/UiO-66 catalyst due to the higher Lewis acidity of the support. Moreover, by using a thermal treatment. The Lewis acidity can be further increased through the creating of missing-linker defects. The resulting defective Pd/UiO-66-NO2 exhibited the highest CPO selectivity and FAL conversion of 96.6% and 98.9%, respectively. In addition, the catalyst was able to maintain a high activity and stability after four consecutive runs. The current study not only provides an efficient catalytic reaction system for the hydrogenative ring-rearrangement of furfural to cyclopentanone but also emphasizes the importance of defect sites.
