GREEN CHEMISTRY
·
2023
·Vol. 25
·期 5
·1823-1834
·
IF 9.8
Ying Duan,Chi Zhang,Dongsheng Deng,Dong Sui,Xiaohan Gao,Yanliang Yang
The rearrangement of furan rings for valuable chemicals is an important topic for biomass conversion. In this study, 2,5-di(hydroxymethyl)furan (BHMF) was selectively converted to 6-methyldihydro-2H-pyran-3(4H)-one (MDPO) and 1-hydroxy-2,5-hexanedione (HHD) under atmospheric H2 pressure in water. The selectivity to MDPO or HHD could be regulated by a catalyst. The parameters (temperature, pH, catalyst loading, and BHMF concentration) for the transformation of BHMF were studied. The selectivity for the transformation of BHMF was very sensitive to the reaction conditions, especially for the conversion of BHMF to MDPO. 68% selectivity to MDPO on Pd/C and 72% selectivity to HHD on Rh/C were achieved under the optimized conditions. Both Pd/C and Rh/C could be reused at least 5 times without the loss of activity. The fresh and used Pd/C and Rh/C were characterized by XRD, XPS, SEM, TEM, EDS mappings and ICP-OES to study the changes during the reaction. The reaction process was studied through controlled experiments, and 6-methylene-2H-pyran-3(6H)-one (MEPO) and 6-hydroxy-6-methyl-2H-pyran-3(6H)-one (HMPO) were identified as intermediates. A reasonable reaction mechanism was proposed and the different selectivity to MDPO and HHD was well explained based on the controlled experiments and DFT calculations. The conditional sensitivity for the selectivity to MDPO and HHD could also be interpreted by the proposed reaction pathway.
研究领域:
化学工程
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生物质能
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催化科学
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产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Yanan Wei,Tao Xia,Tongyu Zhong,Henghui Zhu,Yucai He,Yunlei Zhang
Interface engineering is a significance strategy to afford efficient selective oxidation for supported catalysts. Herein, constructing of frustrated Lewis pairs (FLPs) sites on CeO 2 and supporting Au-Pd nanoparticles to provide a highly selective production of 2,5-furandicarboxylic acid (FDCA) from 2,5-bis(hydroxymethyl)furan (BHMF). Mechanism investigations illustrate that the FLPs active sites enhance the adsorption and activation of catalyst for BHMF, decreasing the activation energy of rate-determining step. Simultaneously, the FLPs sites induce the electron transfer of the catalyst, generating a novel Au-Pd-CeO 2 interface that promotes the adsorption of molecule oxygen and the formation of the superoxide radical. Thereby, the Au x Pd y /P T -CeO 2 catalysts enable superior catalytic performance, achieving a satisfactory turnover frequency of 55.29 h −1 and a highly FDCA yield of 94.0 %. Such interfacial FLPs sites exhibit the great potentials for the selective oxidation of various unsaturated compounds.
研究领域:
化学工程
·
催化科学
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产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2023
·
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
·
2021
·
IF 19.503
Bin Zhu,Chunlin Chen,Liyuan Huai,Zhenqiang Zhou,Lei Wang,Jian Zhang
Simultaneous production of value-added 2,5-furandicarboxylic acid (FDCA) and H 2 from the integrated 5-hydroxymethylfurfural (HMF) oxidation and hydrogen evolution reaction by electrocatalysis has drawn tremendous attention due to the significantly improved energy efficiency. However, HMF is not thermally and chemically stable enough to often cause heavy degradation, impeding its storage and industrialization. In this work, a more stable furan molecule, 2,5-bis(hydroxymethyl)furan (BHMF), was employed as the reaction substrate into the coupling system for the first time. By means of facile electrodeposition and subsequent oxidative activation, the standing CoOOH nanosheet electrocatalyst was fabricated to realize a complete BHMF conversion with 90.2 % FDCA yield and 100 % current efficiency for H 2 evolution. The reaction path and apparent activation energies were therefore discussed. Scalable properties and electrochemical durability of CoOOH were evaluated in a continuous flow reactor to harvest gram-level solid FDCA, highlighting the prospect of green coupling electrolysis for industrial application.
研究领域:
化学工程
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能源科学
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DOI
高影响因子
ChemSusChem
·
2024
·
IF 7.5
Bin Zhu,Qiuge Wang,Jinggang Wang,Xiao Yu,Jian Zhang,Chunlin Chen
Graphical The nitrogen-doped-carbon encapsulated cobalt (Co@NC) chainmail nanowires were synthetized for the electrocatalytic production of 2,5-furandicarboxylic acid (FDCA) from 2,5-bis(hydroxymethyl)furan (BHMF). The Co@NC on Ni foam achieved 97.9 % conversion of BHMF, yielding 93.3 % FDCA at 1.475 V vs. RHE. The superior electrochemical performance of Co@NC/NF can be attributed to its large electrochemically active surface area and excellent kinetic parameters. 2,5-Furandicarboxylic acid (FDCA) has emerged as an important bio-based furanic compound, which has broad application prospects in renewable energy and materials, especially in the preparation of polyethylene 2,5-furandicarboxylate (PEF). While the conventional synthesis of FDCA involves oxidation of 5-hydroxymethylfurfural (HMF) as a substitute, the thermal and chemical instability of HMF due to its aldehyde group poses challenges. A more favorable alternative is the utilization of 2,5-bis(hydroxymethyl)furan (BHMF), a non-aldehyde and more stable precursor. This study pioneeringly reports nitrogen-doped-carbon encapsulated cobalt (Co@NC) chainmail nanowires for the thermal and electrocatalytic oxidation of BHMF to FDCA. The Co@NC/NF achieved a 97.9 % conversion of BHMF with a 93.3 % yield of FDCA at 1.475 V vs. RHE, whereas thermal catalysis only obtained 14.9 % FDCA yield after 10 hours. Kinetic studies indicated that the large electrochemically active surface area and excellent kinetic parameters contribute its superior electrochemical performance. Mechanistic analysis revealed that the migration of inner electrons to the exterior modified the electronic properties of the carbon layer, thereby facilitating the oxidation of BHMF. Furthermore, the in-situ generation of high-valent cobalt species markedly accelerated the BHMF oxidation. This research underscores the potential of carbon-encapsulated metal chainmail catalysts in thermal and electrochemical biomass conversion.
研究领域:
化学
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材料科学
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可再生资源与环境
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产品关联
DOI
PubMed
高影响因子
ChemCatChem
·
2019
·Vol. 11
·期 8
·2179-2186
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IF 4.495
Hualei Hu,Danxin Hu,Haitao Jin,Pilan Zhang,Guozheng Li,Hao Zhou,Yong Yang,Chunlin Chen,Jian Zhang,Lei Wang
Graphical In the reaction zone : Benefiting from the presence of the secondary porosity and the appropriately acidity, the hierarchically structured ZSM-5 (HSZ) catalysts exhibited the excellent catalytic performance for the conversion of 2,5-bis(hydroxymethyl)furan (BHMF) to 2,5-bis(ethoxymethyl)furan (BEMF) in a continuous fixed bed reactor. The highest yield of BEMF (90.46 %) was obtained over the HSZ-150 catalyst under the reaction condition of 140 °C, 2.0 MPa of H 2 , and 0.3 h −1 of WHSV. The selective conversion of 2,5-bis(hydroxymethyl)furan (BHMF) to 2,5-bis(ethoxymethyl)furan (BEMF) was investigated in a fixed bed reactor over several heterogeneous solid acid catalysts, including Amberlyst-15, ZSM-5, Mordenite, and a series of hierarchically structured ZSM-5 zeolites (HSZ). The HSZ catalysts exhibited superior catalytic performance to other three commercial catalysts. The highest yield of BEMF (90.46 %) was obtained over the HSZ-150 catalyst under the reaction condition of 140 °C, 2.0 MPa of H 2 , and 0.3 h −1 of WHSV. Moreover, the HSZ-150 catalyst displayed an extremely good stability in the etherification reaction, maintaining more than 80 % yield of BEMF for about 80 h. The outstanding catalytic performance of the HSZ-150 catalyst could be ascribed to that the presence of mesopores enhanced the etherification activity by alleviating the diffusion limitation, and the appropriate acidity improved the BEMF selectivity via suppressing the side reactions.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Jing Liu,Bin Zhu,Yang Zhong,Shilin Fan,Liyuan Huai,Hualei Hu,Yong Yang,Jian Zhang,Chunlin Chen
Electrocatalysis using 5-hydroxylmethylfurfural (HMF) as a substrate to produce 2,5-furandicarboxylic (FDCA) is a potentially sustainable and mild route to harvest both value-added chemicals and clean energy hydrogen. However, the poor chemical and thermal stability of HMF has impeded its storage and industrialization. Additionally, the uncontrollability, scalability, and cost of catalyst preparation methods are rarely considered in this field. Herein, we capitalize on the spontaneous and harmful corrosion phenomenon occurring under natural conditions to prepare efficient Co-based catalysts for the electrooxidation 2,5-bis(hydroxymethyl)furan (BHMF) with more stable dihydroxy groups, coupled with hydrogen evolution. The preparation of electrocatalysts through corrosion engineering is a straightforward, cost-effective, highly feasible, and scalable approach, requiring minimal equipment. In the optimal concentration of 200 mM BHMF, an ultrahigh current density of 1981.7 mA cm −2 was achieved at 2.293 V vs. RHE, contributed by both BHMF oxidation and oxygen evolution reaction (OER). Chronoamperometric electrolysis realized efficient FDCA production with 95.4% yield and 96.5% faradaic efficiency (FE) at an ultralow potential of 1.4 V vs. RHE. Since it is etched and grown on the substrate itself, the catalyst prepared by corrosion engineering is very stable and undergoes ten successive chronoamperometric electrolysis without significant structural or performance failure. Moreover, kinetic analyses are investigated to explore the origin of catalytic activity and reaction energy barrier. Finally, to further realize the potential of FDCA and H 2 production in practical application, we innovatively designed a device with a two-electrode electrolyzer and a solar cell in series to drive BHMF electrooxidation with outdoor sunlight. The complete conversion of BHMF only takes 90 min, achieving a 93.5% FDCA yield and nearly theoretical hydrogen evolution.
研究领域:
化学工程
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可再生能源
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环境科学
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产品关联
DOI
高影响因子
ChemSusChem
·
2024
·
IF 7.5
Xingyu Luo,Cheng Xie,Zhefei Zhao,Meiqin Shi,Huajun Zheng
Graphical Volcano plots are highly effective for understanding catalyst mechanisms and rational designing high-performance catalysts, particularly across different metals. However, the understanding of the relationship between different metals and their reaction mechanisms in 5-Hydroxymethylfurfural (HMF) reduction reactions is still limited. In this study, we explore the Gibbs free diagram of HMF reduction reactions on different metal surfaces and construct a volcano plot that connects HMF adsorption energy with the energy barriers of the rate-determining step. This provides a deeper understanding of HMFRR. Our theoretical findings align well with experimental results. Furthermore, we selectively constructed an AgPb bimetal interface based on our volcano plot, which boosted the catalyst activity. DFT calculations revealed that the AgPb bimetal surface effectively adjusts HMF adsorption energy and reduces energy barriers, suggesting that rational designing bimetal catalysts based on volcano plots is efficient. 2,5-bis(hydroxymethyl)furan (BHMF) derived from 5-Hydroxymethylfurfural (HMF) through a hydrogenation process has extensive applications in the production of resins, polymers, and artificial fibers. However, screening out the candidate and then modulating the active site to optimize the catalyst for high yield of BHMF are currently insufficient. In this study, Gibbs free energy diagrams of the reduction of HMF on 13 metals were presented, along with the identification of the rate-determining step (RDS) with the highest reaction barrier for each metal. We attempted to construct a volcano plot for HMFRR reaction. Additionally, a strategy was proposed to adjust the reaction barriers of RDS by combining two appropriate metals. Further experiments confirmed that Pb with the lowest energy barrier exhibited the highest HMF conversion (BHMF selectivity) among single metals. The modified catalyst by doping Ag on Pb, further boosted the HMF conversion (BHMF selectivity) from 42.1 % (59.4 %) to 80.8 % (80.9 %), respectively. These results provide an approach to rationally design and construct the catalyst system for efficient conversion of HMF.
研究领域:
催化化学
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材料科学
·
理论计算
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 5.1
Weizhen Xie,Yue Tang,Jiacheng Li,Yaqi Shi,Shigang Su,Yong Sun,Lu Lin,Xing Tang
The aqueous-phase hydrogenation of concentrated 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) is a crucial transformation for sustainable chemical production. However, this process is often limited by sluggish H 2 activation at low temperatures and poor selectivity arising from over-hydrogenation. Here, we develop a Pt catalyst supported on oxygen-deficient manganese oxide (Pt/MnO x –O v ), featuring finely dispersed Pt/PtO 2 domains in conjunction with abundant Pt–O–Mn interfacial ensembles. Under mild aqueous conditions (30–60 °C), the catalyst efficiently converts HMF at concentrations up to 40 wt%, delivering a BHMF yield of 90.9 %. In addition, continuous-flow operation at 30 °C sustains BHMF yields above 90 % over a cumulative operation time of 80 h, thereby demonstrating promising potential for industrial application. Mechanistic studies suggest that hydrogen is initially activated on Pt nanoparticles and subsequently undergoes in situ spillover, migrating across the Pt/PtO 2 heterostructure toward adjacent Pt–O–Mn interfacial sites. At these interfacial regions, the asymmetric electronic distribution, induced by nearby oxygen vacancies, facilitates the formation of polarized H δ+ –H δ- species. These reactive hydrogen species, together with the preferential adsorption of the carbonyl group, enable selective hydrogenation while suppressing undesired side reactions. This study demonstrates that tailoring interfacial structures is an effective strategy for improving catalytic performance in biomass upgrading.
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DOI
高影响因子
CELLULOSE
·
2022
·Vol. 29
·期 8
·4525-4537
·
IF 6.123
Wang Huiqiang,Fang Shengqiong,Zuo Miao,Li Zheng,Yu Xin,Tang Xing,Sun Yong,Yang Shuliang,Zeng Xianhai,Lin Lu
Removal of copper ions (Cu(II)) efficiently from water is crucial for water environment security. We use sustainable, low-cost, renewable cellulose derivatives (carboxymethylcellulose sodium (CMC-Na)) and polyvinyl alcohol (PVA) as the matrix, and cellulose nanocrystals (CNCs) as the functional addition. The CNC/CMC-Na/PVA hydrogel was prepared by the physical cross-linking method. Static adsorption experiments proved that CNC/CMC-Na/PVA hydrogel has a greater adsorption potential (108 mg/g) towards Cu(II). At the same time, the adsorption of Cu(II) on CNC/CMC-Na/PVA hydrogels is spontaneous and endothermic, and obeys the pseudo-second-order model with intra-particle diffusion. Furthermore, the primary adsorption mechanisms had been electrostatic attraction and surface complexation. Importantly, CNC/CMC-Na/PVA hydrogel has efficient absorbability and preferable reusability in actual water samples. Furthermore, the copper nanoparticles (Cu NPs) adsorbed on the surface of CNC/CMC-Na/PVA hydrogels were reduced with NaBH 4 in situ to realize the secondary utilization in CNC/CMC-Na/PVA hydrogels supported by Cu NPs. It is found that the material can be used as a catalyst to efficiently catalyze the conversion of HMF to BHMF (99%). Consequently, we provide insights into the hydrogel preparation that would possibly be promising novel adsorbents for the elimination of heavy-ion from sustainable water purification. Graphical abstract
研究领域:
环境科学
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材料科学
·
化学工程
·
水处理
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2022
·Vol. 24
·期 22
·8691-8704
·
IF 11.034
Xin Pan,Xue Wang,Sihua Wu,Lei Xu,Leilei Zhang,Zhan Zhang,Bingfeng Li,Xuejun He,Siyuan Chang
Upgrading of the bio-based platform chemical 5-hydroxymethylfurfural (HMF) into high-value derivatives is an important research topic, particularly in green and sustainable chemistry. Herein, we applied a new, highly HMF-tolerant strain, Enterobacter ludwigii YYP3, as a whole-cell biocatalyst for efficient reduction of HMF to 2,5-bis(hydroxymethyl)furan (BHMF). Upon process optimization, within only 3 h, BHMF was produced with a yield >99% and 98.5% selectivity using 100 mM HMF, resulting in the highest space time yield (4.2 g L−1 h−1) among the currently reported HMF bioreduction processes. In a fed-batch conversion, E. ludwigii YYP3 achieved large-scale production of 290 mM BHMF within 9 h and retained its high catalytic activity for three runs (27 h), suggesting an excellent cycling stability. Based on genome and transcriptome analysis, the molecular mechanism underlying the high HMF tolerance of E. ludwigii YYP3 was explored, primarily through the downregulation of genes related to amino acid biosynthetic and metabolic processes and upregulation of genes associated with DNA replication, recombination, and repair; biofilm formation; and redox homeostasis. Meanwhile, two novel short-chain dehydrogenase/reductase family oxidoreductases ElSDR-ykvO and ElSDR-SSP1627 were identified as target enzymes responsible for conversion of HMF to less toxic BHMF in E. ludwigii YYP3. Combined with structure and mutation analysis, the catalytic mechanisms of target enzymes were determined to be based on the active sites Ser, Tyr, and Lys. Our work not only confirms that E. ludwigii YYP3 has promising application prospects in large-scale production of BHMF, but also provides novel insights into understanding the molecular mechanism of HMF reduction.
研究领域:
生物催化
·
生物化学工程
·
分子生物学
·
绿色化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）