97-99-4Relevant articles and documents
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.
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.
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.
Craig et al.
, p. 3277 (1950)
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.
Hydrogenolysis of Furfuryl Alcohol to 1,2-Pentanediol Over Supported Ruthenium Catalysts
Yamaguchi, Aritomo,Murakami, Yuka,Imura, Tomohiro,Wakita, Kazuaki
, p. 731 - 736 (2021/06/12)
Hydrogenolysis of the furan rings of furfural and furfuryl alcohol, which can be obtained from biomass, has attracted attention as a method for obtaining valuable chemicals such as 1,2-pentanediol. In this study, we examined the hydrogenolysis of furfuryl alcohol to 1,2-pentanediol over Pd/C, Pt/C, Rh/C, and various supported Ru catalysts in several solvents. In particular, we investigated the effects of combinations of solvents and supports on the reaction outcome. Of all the tested combinations, Ru/MgO in water gave the best selectivity for 1,2-pentanediol: with this catalyst, 42 % selectivity for 1,2-pentanediol was achieved upon hydrogenolysis of furfuryl alcohol for 1 h at 463 K. In contrast, reaction in water in the presence of Ru/Al2O3 afforded cyclopentanone and cyclopentanol by means of hydrogenation and rearrangement reactions.
Ru Nanoparticles on a Sulfonated Carbon Layer Coated SBA-15 for Catalytic Hydrogenation of Furfural into 1, 4-pentanediol
Cui, Kai,Qian, Wei,Shao, Zhengjiang,Zhao, Xiuge,Gong, Honghui,Wei, Xinjia,Wang, Jiajia,Chen, Manyu,Cao, Xiaoming,Hou, Zhenshan
, p. 2513 - 2526 (2021/02/05)
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.].