GREEN CHEMISTRY
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2025
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IF 9.2
Xiaodie Zhang,Bin Liu,Yuchen Wang,Ying Long,Zhenhao Xu,Hua-Tay Lin,Rafael Luque,Kai Yan
Electrocatalytic dimerization (ECD) of biomass platform molecules represents a promising route for sustainable fuel and chemical production. However, the widespread application of ECD is limited by catalysts with low activity, undesired product selectivity and poor durability. Herein, we demonstrate the development of high-performing and stable transition metal borides WMoB nanoflakes catalyst for the ECD of biomass-derived furfural (FF) into hydrofuroin (HFN) which is a precursor of jet fuel. As-obtained WMoB nanoflake-likes electrocatalyst, prepared by solvent-free mechanical alloying strategy, could achieve FF conversion of 80.5% and an HFN selectivity of 76.7% at −0.59 V vs. RHE (Reversible Hydrogen Electrode), which is 3.7 times more selective than WB for HFN (20.4%). Experimental and theoretical studies, including X-ray absorption fine structure (XAFS), electrochemical analysis, in situ electron paramagnetic resonance (EPR), kinetic isotope effect (KIE) evaluation and density functional theory (DFT) calculations reveal that high coverage of furan radicals on WMoB nanoflakes play a crucial role for the ECD reaction. The furan radicals-driven C–C coupling reaction offers an alternative strategy to synthesize valuable products from biomass refineries.
研究领域:
可再生能源化学
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催化化学
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DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
·
IF 9.7
Songtao Guo,Junhao Ren,Jiuli Chang,Yan Hou,Xiaoming Ma,Zhiyong Gao
Furfural (FF) is a biomass-derived platform molecule characterized by an aldehyde group attached to a furan ring. The selective electrochemical hydrogenation (ECH) of the aldehyde group into hydroxymethyl offers a sustainable approach for converting FF into valuable furfuryl alcohol (FA) chemical. Efficient catalyst that balances active hydrogen (H*) generation and FF adsorption is crucial for electrochemical FF-to-FA conversion. Herein, a self-supported copper oxide (CuO 1-x ) with mixed Cu oxidation values was fabricated onto Cu foam substrate (CuO 1-x /CF) via facile electrodeposition and was investigated as a catalytic electrode for ECH of FF to FA. Under optimal condition, the electrocatalytic system achieved a maximized faradaic efficiency (FE) of 83 % and a selectivity of 95 % for FA synthesis at a cathodic current density ( J ) of −20 mA cm −2 . Electrochemical in situ Raman spectroscopy, H* detection, and thiol passivation experiments revealed the ECH pathway for FF conversion. In this progress, the H* generated via water dissociation reacts with adsorbed FF to afford FA with high FE and selectivity over CuO 1-x /CF. In situ X-ray diffraction (XRD) characterizations evidenced that the reductive reconstruction of CuO 1-x active layer into Cu metal under negative potential, which enhances the generation of H* and facilitates the ECH of adsorbed FF to FA. Furthermore, pairing the cathodic ECH of FF with anodic magnesium (Mg) oxidation reaction constituted a Mg-FF battery, which enabled electricity output at a high power density (3.7 mW cm −1 ) during FA electrosynthesis. This work offers essential instruction for electrochemical valorization of biomass-derived FF molecule, and showcases a viable paradigm for construction of metal-organic battery to concurrently generate electricity and value-added chemicals.
研究领域:
电化学
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催化
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生物质转化
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材料科学
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可持续化学
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储能
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DOI
PubMed
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
·
IF 17.7
Wanying Liang,Guangyue Xu,Yao Fu
Transition-state shape selectivity plays a crucial role in catalytic systems where reactants and products exhibit comparable molecular dimensions, as it restricts the accessible configuration space of reaction intermediates. Herein, we designed a Cu@MFI catalyst by encapsulating Cu active sites within the well-defined micropores of MFI zeolite through a pore confinement strategy. This architecture preserves the zeolite framework integrity while maintaining unhindered internal mass transport, thereby enabling precise spatial control over transition-state configurations. Employing furfural hydrogenation as a probe reaction, the metal-zeolite synergy in Cu@MFI endowed the catalyst with exceptional activity (100% furfural conversion) and quantitative selectivity (100% furfuryl alcohol) at 70 °C, sustained across a broad temperature window. Mechanistic studies reveal that the transition-state shape selectivity effectively prevented H 2 O interaction with the furan ring, offering valuable insights for other reaction systems seeking to exploit shape selectivity for specific transformations.
研究领域:
催化
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化学反应工程
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材料科学
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绿色化学
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Luyao Li,Rundong Wu,Jianhua Guo,Mengrong Han,Shiji Guo,Weiping Chen,Gang Feng,Xinwu Ba,Xin Wen
Furfural-based bifuran diacids/diesters, such as 2,2′-bifuran-5,5′-dicarboxylic acid (BFDCA), are important biomass-derived chemicals in the production of high-performance polymers and plasticizers. However, the synthesis of bifuran diacids/diesters lacks an efficient heterogeneous catalytic system. Here, we report that the interstitial modification of a PdNi bimetallic nanoalloy with boron atoms supported on nitrogen-doped carbon exhibited high catalytic efficiency in the conversion of halogenated furoic acids/esters to bifuran diacids/diesters via sequential oxidative addition and reductive elimination steps initiated at room temperature, affording a high yield with a Pd/Ni molar ratio of 1:1. The conversion of 5-bromo-2-furoic acid to BFDCA has a turnover frequency value of up to 672.0 h–1, 2.5 times higher than that of commercial Pd/C. The comprehensive characterization results demonstrated that boron as an interstitial atom entered into the lattice of the PdNi alloy, leading to lattice distortion and the regulation of the electronic state of Pd. Density functional theory calculations exhibited that these electronegative Pd sites were pivotal active species in the oxidation addition, where Ni facilitated the coordination of Pd and carbon–halogen bonds. The optimal catalyst showed excellent stability and recyclability in alkaline aqueous solution. This protocol provides an efficient strategy for the reductive homocoupling and sustainable production of bifuran diacids/diesters and their derivatives from biomass resources.
研究领域:
催化化学
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材料化学
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可持续化学
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生物质转化
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纳米材料
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有机合成
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DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Quanxing Zhang,Caoying Kang,Zhaozhe Li,Kerui Hua,Dongpei Zhang,Wei Yu,Xin Jin,Chaohe Yang
Glutaric acid, a C 5 dicarboxylic acid, servers as an essential monomer in nylon industry. Currently, it is primarily obtained as a byproduct of adipic acid production. Green synthesis of glutaric acid from bio-resources remains a grand challenge. Here, we present a two-step synthesis of glutaric acid from furfural via cyclopentanone as the key intermediate. In the first step, a series of Ni modified CuO x catalysts derived from HKUST-1 (Cu) displays a record conversion rate (20.8 h −1 at 140 ℃) in converting furfural to cyclopentanone, with 99.8 % conversion of furfural and 87.4 % selectivity to cyclopentanone. The d-d orbital coupling between Ni and Cu through the oxygen bridge bond leads to an upshifted d band center of Cu sites, inducing the σ-bonding between the e g orbital of the electron-deficient Cu 2+ and C=O bond of furfural. In the second step, the C=O bond of cyclopentanone can be activated effectively over electron-rich Cu 2+ sites of HKUST-1 (Cu). The oxidation of cyclopentanone to glutaric acid was achieved on heterogeneous catalyst for the first time, with 40 % and 17.6 % yield of glutaric and succinic acids, respectively. The reaction mechanism has also been proposed. DFT calculation has revealed that 1,1,2-trihydroxy-cyclopentane is an important intermediate product, with proton removal to form C-O· radical as the rate-determining step. This work provides insights into the synthesis of bio-glutaric acid through a chemocatalytic route.
研究领域:
催化
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绿色化学
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有机合成
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材料科学
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化学工程
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DOI
高影响因子
Catalysts
·
2026
·Vol. 16
·期 3
·264
·
IF 4.5
Chenfeng Li,Jiahao Ju,Beizhan Li,Jilei Xu,Xin Su,Zuoyi Xiao,Qingda An,Jiahui Huang
5-Methoxymethyl-2-furfural (MMF) serves as a crucial biobased platform molecule that can be transformed into various high-value chemicals and biobased polyester monomers. However, the current production of MMF still faces several challenges, such as low yield and prolonged reaction time. In this study, we prepared a series of amide-modified strongly acidic resin catalysts and discovered that they have a higher efficiency in converting fructose to prepare MMF in 1-Butyl-3-methylimidazolium chloride ([BMIM]Cl) and methanol. Among the synthesized catalysts, DB757-NMP demonstrated superior performance, achieving an MMF yield of approximately 61.5% under the optimized conditions, with a combined yield of HMF and MMF reaching about 66.6%. The catalyst formation mechanism was analyzed using FTIR, and NMR, confirming the transformation of proton between NMP and the sulfonic acid groups of the resin, which collectively promoted the conversion of fructose to MMF. In addition, we investigated main reasons for catalyst deactivation and successfully restored catalytic activity through regeneration. The regenerated catalyst could be reused for three times with only a slight decrease in MMF yield. The results suggested that DB757-NMP is a more sufficient and recyclable catalyst for the production of MMF from fructose. This work presented a simple and environmentally benign approach for the synthesis of MMF.
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高影响因子
FUEL
·
2021
·
IF 6.609
Bin Hu,Wen-luan Xie,Yu-ting Wu,Ji Liu,Shan-wei Ma,Ti-peng Wang,Shu Zheng,Qiang Lu
Furfural (FF) is a promising platform compound that can be selectively produced by the fast pyrolysis of xylan-based biomass in the presence of zinc chloride (ZnCl 2 ). Whereas, the catalytic effect of ZnCl 2 and the FF formation mechanism remain uncovered. The present work aims to give a deep insight into the formation mechanism of FF under the catalysis of ZnCl 2 by combining quantum chemistry calculations and fast pyrolysis experiments. Density functional theory (DFT) calculations and fast pyrolysis experiments were conducted with xylose as the model compound. ZnCl 2 affects the pyrolysis reactions through the binding of Zn atom and O atom of xylose initially, with manifest electron exchange between Zn and O. The activation free energies of the pyrolysis reactions can be decreased when ZnCl 2 stays at the reaction center of the transition states. Both ring-opening and 1,2-dehydration can be promoted by ZnCl 2 , whereas ring-contraction is hindered by ZnCl 2 because ZnCl 2 is away from the reaction center of the ring-contraction. Due to the distinct influence of ZnCl 2 on different reactions, the rate-determining steps in some of the possible FF formation pathways are changed. Hence, the competitiveness of these pathways is altered to a great degree, which should be responsible for the selective production of FF. Xylose tends to generate FF through the acyclic d -xylose decomposition channel due to the catalysis of ZnCl 2 . The most favorable FF generation pathway involves the successive cyclization, 1,2-dehydration between 2-OH and 1-H, electrocyclic dehydration, and 1,2-dehydration between 4-OH and 5-H following the formation of a d -xylulose intermediate.
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ENERGY & FUELS
·
2021
·
IF 3.605
Hao Xu,Shanshan Xiong,Yuan Zhao,Lingjun Zhu,Shurong Wang
Furfural is an important platform chemical that can be produced by dehydration of pentose, which is an important building block of lignocellulosic biomass. In this study, xylose was chosen as the reaction substrate, and a carbon-based solid acid prepared from pectin was used as the catalyst in a mixed solvent consisting of water and γ-valerolactone (GVL). FTIR results showed that the sulfonated catalyst had typical characteristic peaks of sulfonic groups, while the results based on NH3-TPD and elemental analysis showed that the sulfonation temperature changed the surface acid concentration and acid site intensity of the catalyst. A furfural yield of 80.4% and a xylose conversion of 100% were obtained at 170 °C for 60 min. The conversions and product yields were influenced by the reaction temperature, reaction time, solvent composition, and catalyst acidity. Different sulfonation temperatures can change the acidity of the catalyst, which determines the catalytic performance of the catalyst.
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高影响因子
RSC Advances
·
2021
·Vol. 11
·期 6
·3280-3287
·
IF 3.361
Defeng Yin,Yanxia Zheng,Lixi Yang,Shuyue Li,Daqing Zhu,Yafei Guo,Cuncun Zuo,Yuchao Li,Haofei Huang,Ming Wang
A series of highly dispersed cobalt-based catalysts on N-doped ordered porous carbon (Co-NOPC) were synthesized using the sacrificial-template method. MCM-41, ZSM-5 and SBA-15 were employed as hard templates with 2,2′-bipyridine as the ligand. The physical and chemical properties of the Co-NOPC catalyst were characterized by Raman, XRD, SEM, TEM, EDX, ICP, BET, XPS. Co-NOPC had been proven to be a highly efficient catalyst for oxidative esterification of furfural (FUR) to methyl 2-furoate without alkaline additives. Catalytic performance was correlated to the dispersed cobalt, porous structure and specific surface area. The relationship between oxygen activation and the strong interaction of cobalt and pyridine nitrogen were confirmed by XPS. Catalytic performance enhancement mechanisms were correlated with the redistribution of electrons at the interface between carbon material and cobalt atoms through the molecular dynamics method and a reaction mechanism was also proposed. The optimized catalysts showed outstanding catalytic activity and stability and no obvious decrease in activity was found after 6 cycles with 99.6% FUR conversion and 96% methyl 2-furoate selectivity.
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DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2020
·
IF 16.683
Wei Liu,Yusen Yang,Lifang Chen,Enze Xu,Jiaming Xu,Song Hong,Xin Zhang,Min Wei
Activation of oxygen-containing functional groups plays a key role in sustainable biomass upgrading and conversion. In this work, a NiMo intermetallic compound (IMC) catalyst was prepared based on layered double hydroxides (LDHs) precursors, which displayed prominent catalytic performance for furfural hydrodeoxygenation (HDO) to 2-methylfuran (2-MF) (yield: 99 %) at a rather low hydrogen pressure (0.1 MPa), significantly superior to NiMo alloy, monometallic Ni and other Ni-based catalysts ever reported. CO-IR, STEM, EXAFS and XANES give direct evidences that the atomically-ordered Ni/Mo sites in NiMo IMC determine the uniform bridging-type adsorption mode of C O bond in furfural whilst adsorption of furan ring is extremely suppressed. In situ FT-IR and DFT calculation further substantiate that ordered Ni-Mo bimetallic sites of IMC, in contrast to the random atomic sequence in NiMo alloy, facilitate the activation and cleavage of C OH bond in the intermediate (furfuryl alcohol, FOL), accounting for the production of 2-MF. This work demonstrates the decisive effect of atomically-ordered active sites in IMC catalyst on activation of oxygen-containing functional groups and product selectivity, which can be extended to catalytic upgrading of biomass-derived platform molecules.
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Catalysts
·
2020
·Vol. 10
·期 11
·1304
·
IF 3.52
Qiang Yuan,Jifeng Pang,Wenguang Yu,Mingyuan Zheng
A high-performance Pt catalyst supported on SBA-15 was developed for furfural decarbonylation. Compared to Pt catalysts loaded on microporous DeAl-Hbeta zeolite and hierarchical micro-mesoporous MFI nanosheet (NS) materials, the 1%Pt/SBA-15 catalyst afforded notably higher activity, furan selectivity and stability owing to the negligible acid sites and proper mesopores on the SBA-15 support. Among a set of 1%Pt/SBA-15 catalysts bearing Pt nanoparticles (NPs) with sizes of 2.4–4.3 nm, the catalyst with 3.7 nm Pt NPs afforded the highest furan selectivity. Over the optimal catalyst, 88.6% furan selectivity and ca. 90% furfural conversion were obtained at 573 K and a high weight hourly space velocity (WHSV) of 16.5 h−1. Moreover, the reaction temperatures at 440–573 K and the ratios of H2to furfural at 0.79–9.44 did not affect the reaction selectivity notably, showing that the reaction over 1%Pt/SBA-15 can be conducted over a wide range of conditions. The catalyst was stable under the harsh reaction conditions and lasted for 90 h without significant deactivation, demonstrating the superior property of SBA-15 as a catalyst support for furfural decarbonylation.Keywords:decarbonylation;furfural;furan;platinum;SBA-15
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ACS Sustainable Chemistry & Engineering
·
2020
·
IF 7.632
Xiaoqi Wang,Mo Qiu,Richard Lee Smith Jr.,Jirui Yang,Feng Shen,Xinhua Qi
Ferromagnetic Ni-doped lignin-derived ordered mesoporous carbon (Ni@OMC) was synthesized in one pot by evaporation-induced self-assembly (EISA) for use as catalysts. Lignin was used to partially replace phloroglucinol (up to 80%) as the carbon precursor under conditions that allowed ordered mesoporous structures to be perfectly retained and Ni particles to be uniformly dispersed within the material. The as-synthesized Ni@OMC catalysts promoted hydrogenation of furfural, affording furfuryl alcohol (FAL) yields and selectivities as high as 91.0 and 98.6% at 180 °C for a 12 h reaction time in the presence of H2 gas. The Ni@OMC catalyst could be simply separated through application of a magnetic field and was recyclable for at least five cycles. The stability of the Ni@OMC catalyst is attributed to space confinement effects of the carbon skeleton on the doped Ni particles through coordinated interactions between lignin and metal ions (Ni2+). The proposed method allows the synthesis of metal-doped ordered porous carbons from lignin and is green and sustainable.
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高影响因子
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