Journal of Energy Chemistry
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2023
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IF 13.1
Mengxia Li,Tianxi Zheng,Dongfei Lu,Shiwei Dai,Xin Chen,Xinchen Pan,Dibo Dong,Rengui Weng,Gang Xu,Fanan Wang
The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventional thermocatalytic route for the production of high-value-added chemicals from biomass resources. In virtue of the wide potential window with promising Faradic efficiency (FE) towards BHMF, Cu-based electrode has been in the center of investigation. However, its structure–activity relationship remains ambiguous and its intrinsic catalytic activity is still unsatisfactory. In this work, we develop a two-step oxidation–reduction strategy to reconstruct the surface atom arrangement of the Cu foam (CF). By combination of multiple quasi-situ/in-situ techniques and density functional theory (DFT) calculation, the critical factor that governs the reaction is demonstrated to be facet effect of the metallic Cu crystal: Cu(110) facet accounts for the most favorable surface with enhanced chemisorption with reactants and selective production of BHMF, while Cu(100) facet might trigger the accumulation of the by-product 5,5′-bis(hydroxymethy)hydrofurion (BHH). With the optimized composition of the facets on the reconstructed Cu(OH) 2 -ER/CF, the performance could be noticeably enhanced with a BHMF FE of 92.3% and HMF conversion of 98.5% at a potential of −0.15 V versus reversible hydrogen electrode (vs. RHE) in 0.1 M KOH solution. This work sheds light on the incomplete mechanistic puzzle for Cu-catalyzed electrochemical hydrogenation of HMF to BHMF, and provides a theoretical foundation for further precise design of highly efficient catalytic electrodes.
研究领域:
化学工程
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催化科学
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材料科学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
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IF 22.1
Zhaohui Yang,Baolong Zhang,Chuanyu Yan,Zhimin Xue,Tiancheng Mu
Electrochemical oxidation is a promising method to convert 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) with high selectivity at room temperature. Developing catalysts with high current densities is crucial for the industrial application of HMF electrooxidation reaction (HMFOR). Herein, we demonstrate that the current densities exhibited by the LSV curves are falsely high and propose to evaluate catalyst activity using anodic peak current density rather than overpotential for the comparison of actual efficiency. Besides, the reduction of Ni 3+ to Ni 2+ accompanied by proton coupled electron transfer (PCET) process of HMF dehydrogenation is confirmed as the rate-determining step affecting the conversion efficiency of HMF rather than Ni 2+ electrooxidated to Ni 3+ . Theoretical calculations reveal differences in the hydrogen transfer energy barriers of PCET process. Furthermore, Ni(OH) 2 /NF with appropriate Cr doping shows superb activity with actual current densities of over 230 mA cm −2 at HMF concentrations of 10 mM and over 360 mA cm −2 at 20 mM (the ever highest current densities for HMFOR), and obtain a yield of more than 98% of FDCA.
研究领域:
电化学
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催化材料科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
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2025
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IF 4.3
Yaping Liu,Chao Pan,Xianjie Li,Hailin Zhang,Zhijie Shang,Hongbing Song
Oxidation, a pivotal process in organic synthesis, is essential for the conversion of various biomass derivatives, including 5-hydroxymethylfurfural (HMF), into valuable chemicals. This research employs poly(ionic liquid)s (PILs) as supports to fabricate Au/PILs catalysts, which are subsequently utilized in the oxidative esterification of HMF to produce dimethyl 2,5-furandicarboxylate (FDMC). The modification of PILs demonstrates that catalyst’s performance is optimized when the PILs anion (IL: EGDMA = 1: 4) is [Tf 2 N - ]. The presence of the [Tf 2 N - ] group is essential for charge transfer between the carrier and the active metal Au, thereby enhancing the catalytic reaction. Thermogravimetric analysis (TG) reveals the exceptional thermal stability of the 2 % Au/PILs-Tf 2 N-14 catalyst. The efficient conversion of HMF to FDMC is achieved using the 2 % Au/PILs-Tf 2 N-14 catalyst at 120°C, 12 h, with CH 3 ONa (0.75 equiv.) and 2 MPa O 2 , yielding a HMF conversion ( C HMF ) of 96.41 % and a FDMC selectivity ( S FDMC ) of 100 %. The heterogeneous catalyst 2 % Au/PILs-Tf 2 N-14 maintains high catalytic activity after multiple cycling experiments. A catalyst based on precious metal-loaded PILs was utilized to achieve efficient and selective conversion of HMF to FDMC under low loading conditions. This approach not only offers valuable insights for future research but also promotes the shift towards renewable energy sources. Additionally, the adsorption behavior of O 2 on Au 8 clusters and the interaction between the reaction substrate HMF and [Tf 2 N - ] were examined through density functional theory (DFT) calculations, providing theoretical backing for further investigation.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
Catalysis Science & Technology
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2014
·Vol. 5
·期 2
·1314-1322
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IF 4.76
Zhenzhen Miao,Yibo Zhang,Xiqiang Pan,Tianxiao Wu,Bin Zhang,Jingwei Li,Ting Yi,Zhendong Zhang,Xiangguang Yang
Porous Bi-doped ceria (Ce1−xBixO2−δ solid solution) was prepared by the easy citrate method and then used as a supporting material for Au nanoparticles (NPs) obtained by deposition–precipitation. In the presence of O2, Ce1−xBixO2−δ (0.08 ≤ x ≤ 0.5) efficiently catalyzed the conversion of 5-hydroxymethylfurfural (HMF) to 5-hydroxymethyl-2-furancarboxylic acid (HFCA) and 2,5-bishydroxymethylfuran (BHMF) in alkaline aqueous solution without degradation of HMF. The excellent catalytic activity was attributed to the oxygen activation and hydride transfer enhanced by Bi doping and the large amount of oxygen vacancies. After Au NPs were supported on Ce1−xBixO2−δ (x ≤ 0.2), the presence of Auδ+ facilitated the activation of the C–H bond in the hydroxymethyl group and then the production of 2,5-furandicarboxylic acid (FDCA) as an end product, inhibiting the generation of BHMF.
研究领域:
催化
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材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2021
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IF 19.503
Ming Zhang,Zhihao Yu,Jian Xiong,Rui Zhang,Xinzhong Liu,Xuebin Lu
The Cd x In y S ( x +1.5 y ) catalysts with gradient Cd:In ratios were controllably synthesized via an one-step hydrothermal approach. Particularly, the hydrothermal synthesis conferred those Cd x In y S ( x +1.5 y ) catalysts with Cd:In ratios over 1:2 with a one-dimensional–three-dimensional heterojunction structure composed of CdS nanorods and cubic-phase CdIn 2 S 4 . Our characterization evidences reflected that the CdS nanorods effectively promoted the separation of photoexcited electron–hole pairs in Cd x In y S ( x +1.5 y ) and enabled transboundary transfer of photogenerated carriers. Spectroscopic and experimental results were further employed to develop a detailed catalytic mechanism, in which the superoxide anion (•O 2 − ) plays an important role in the catalytic oxidation of HMF to DFF by Cd x In y S ( x +1.5 y ) . Unlike other photocatalysts with •O 2 − as the main active species, Cd 1.5 In 2 S 4.5 gives an excellent performance in HMF conversion. This shows the great potential of cadmium–indium sulfides as photocatalysts for biomass conversion under ambient conditions.
研究领域:
材料科学
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化学工程
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环境科学
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催化
✓ 已验证
产品关联
DOI
高影响因子
Journal of the Taiwan Institute of Chemical Engineers
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2015
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IF 3
Shuguo Wang,Bing Liu,Ziliang Yuan,Zehui Zhang
In this study, magnetic γ-Fe 2 O 3 @ HAP-Mo catalyst was successfully prepared and characterized. The activity of the as prepared γ-Fe 2 O 3 @ HAP-Mo catalyst was evaluated by the oxidation of 5-hydroxymethylfurfural (HMF) with molecular oxygen. Some important reaction parameters were investigated and it was found that both the solvent and the reaction temperature showed great effect on HMF conversion and products selectivity. The highest HMF conversion of 95.8% was obtained in 4-chlorotoluene at the reaction temperature of 120 °C for 12 h, and the corresponding 2,5-diformylfuran, 2,5-furandicarboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid yields were 67.5, 19.6 and 8.7%, respectively. The γ-Fe 2 O 3 @ HAP-Mo catalyst could be easily separated from the reaction mixture and reused several times without the loss of its catalytic activity.
研究领域:
催化
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化学工程
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有机化学
✓ 已验证
DOI
高影响因子
CHINESE JOURNAL OF STRUCTURAL CHEMISTRY
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2023
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IF 2.2
Ke Wang,Jia Wu,Shuyi Zheng,Shibin Yin
Construction of highly active and stable bifunctional catalysts for 5-hydroxymethylfurfural oxidation reaction (HMFOR) and hydrogen evolution reaction (HER) is meaningful but remains a challenge. Herein, the NiCo–Mo 2 N heterostructure nanosheets catalyst with excellent HMFOR/HER performance is obtained by a simple hydrothermal and calcination method. The heterogeneous interface between NiCo and Mo 2 N induces electron redistribution, regulating the electronic structure of the catalyst and thus optimizing the adsorption/desorption behavior of HMFOR/HER intermediates. Consequently, NiCo–Mo 2 N/NF exhibits superior catalytic activity with a potential of 1.14 V RHE /−17 mV RHE (HMFOR/HER) at ±10 mA cm −2 , and the HMF conversion rate, FDCA yield, and Faradaic efficiency (FE) are ∼100%, 99.98%, and 98.65%, respectively. Besides, it only requires a low voltage of 1.36 V to achieve 100 mA cm −2 for HMFOR-assisted H 2 production. This study provides a strategy for the development of efficient bifunctional catalysts for sustainable production of high value-added products and hydrogen.
研究领域:
催化
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电化学
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材料科学
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可持续化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）