JOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE
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2022
·Vol. 102
·期 15
·7249-7258
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IF 4.125
He Li,Fu-Han Yang,Wen-Chao Zhang,Zhi-Jun Zhang,Shu-Juan Yu
BACKGROUND 2,3-Dihydro-3,5-dihydroxy-6-methyl-4( H )-pyran-4-one (DDMP) and 5-hydroxymethylfurfural (HMF) are two main enolization products in the Maillard reaction and found in some foodstuffs. For many years, whether they are functional or noxious to human health has been a matter of debate. Thus, insight into their formation pathways is important to manage Maillard reaction products. In this study, DDMP and HMF were quantified and compared with regard to their formation and degradation in the d -glucose and l -proline Maillard reaction models using different moisture contents (0, 0.1, 0.5, 1.0, and 4.0 mL) at 150 °C for various heating times. RESULTS DDMP was predominantly generated in dry or low water-content heating models along with n increased 1-deoxyglucosone (1-DG) generation via 2,3-enolization. However, increasing moisture content resulted in a decay of reaction intensity, 1-DG, and DDMP due to a change in the reaction mechanism from 2,3-enolization to 1,2-enolization, which facilitated 3-deoxyglucosone (3-DG) and HMF formation. CONCLUSION Increased moisture content in glucose–proline models reduced reaction intensity and also inhibited DDMP and facilitated HMF formation by promoting the pathway change from 2,3-enolization to 1,2-enolization to generate more 3-DG. A water content of 1.0 mL was identified as a critical value, from which the 1,2-enolization became a primary pathway occurring in the Maillard reaction. © 2022 Society of Chemical Industry.
研究领域:
食品科学
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生物化学
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PubMed
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
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2026
·
IF 5.4
Xingyu Hu,Zhiyong Li,Xiaoge Li,Xiangyan Ji,Jingjing Meng
A highly conjugated biobased liquid HPE monomer was fabricated from HMF. • The benzimidazole motif HPE contributes to a relatively mild curing behavior. • The HPE endows the resin with favorable mechanical properties and dimensional stability. • The HPE networks showed good solvent resistance and shape memory. • This strategy provided a tractable biocomposite fabrication. A novel bio-based epoxy monomer (HPE) bearing a rigid benzimidazole-furan skeleton was synthesized from 5-hydroxymethylfurfural (5-HMF). The activation energy for HPE-derived networks was relatively lower than that of the DGEBA counterparts, indicating favorable curing conditions. The cured HPE-thermosets exhibited exceptional mechanical properties. For instance, HPE/APB achieved good tensile strength (105.67 ± 13.43 MPa), flexural strength (125.43 ± 16.65 MPa), and impact strength (17.99 ± 1.10 kJ m −2 ). Moreover, the thermomechanical investigation also suggested its advantageous storage modulus of 3.55 GPa at 30 °C, which surpassed the petroleum-based DGEBA counterparts. Notably, HPE-networks displayed unique dimensional stability with a thermal expansion coefficient ranging from 87 to 115.4 ppm °C −1 below 200 °C. In contrast to DDM-cured thermoset, APB-cured networks also favored decreasing dielectric constant and loss. On the whole, the APB hardener outperformed the DDM in most cases. Furthermore, glass fiber-reinforced HPE composites demonstrated 90.8% peeling off in DMF under microwave-assisted conditions, making sustainable fiber recycling possible. This work provides a promising strategy for HMF-related renewable epoxy resins. Download: Download high-res image (147KB) Download: Download full-size image
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Nature Communications
·
2026
·
IF 18.1
Hu Zhong-Ting,He Gan,Tao Xiaohuan,Tian Jinshu,Tan Mingwu,Ouyang Ni,Li Jun-Long,Hu Mian,Wang Jie-Xin,Zhu Yihan,Cao Dapeng,Pan Zhiyan,Wang Yong,Li Xiaonian
The catalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid is a key step in the production of bio-based plastics but remains limited by sluggish multi-electron transfer kinetics across multiple reaction intermediates. In this study, we address this long-standing challenge by introducing a Mn-O-Co electron bridge within spinel CoMn 2 O 4 to mediate and accelerate electron transfer. Through precise valence state regulation, we engineer a heterogeneous electron bridge dominated by Mn 4+ -O 2- -Co 3+ linkages, enabling more efficient electron flow. Experimental characterization and theoretical calculations reveal that the incorporation of Mn 4+ significantly enhances electron delocalization across the bridge. The empty e g orbitals of Mn 4+ ( t 2g 3 e g 0 ) serve as efficient electron acceptors, creating an energy-level gradient with Co 3+ ( t 2g 4 e g 2 ) that favors directional electron transfer. Simultaneously, Mn 4+ strengthens metal-oxygen covalency, further improving electron mobility. This engineered electron bridge structure enables highly efficient cooperation across the full six-electron transfer pathway in 5-hydroxymethylfurfural oxidation, driven by a dynamic electron compensation mechanism. As a result, an 2,5-furandicarboxylic acid yield of 98.1% is achieved. This work offers a valuable theoretical foundation for understanding cooperative electron transfer in heterogeneous catalysis and provides a rational strategy for designing efficient electron bridge structures.
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Catalysts
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2026
·Vol. 16
·期 3
·214
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IF 4.5
Yuanhua He,Nengfeng Gong,Li Dong,Shanshan Liu,Yong Yang,Yulei Zhu,Yafang Li,Jiale Song,Guoqiang Ding
A series of nickel phyllosilicate catalysts (Ni-PS-T, where T represents the calcination temperature in °C) were synthesized via he ammonia-evaporation method and calcined at different temperatures to investigate their performance in the hydrogenation of 5-hydroxymethylfurfural (HMF). Characterization by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) revealed that increasing the calcination temperature (300–1100 °C) triggered a phase evolution from the 1:1-type (tetrahedral-octahedral) to the 2:1-type (tetrahedral-octahedral-tetrahedral) Ni-PS, eventually leading to phase separation into NiO and SiO2. The content of the 2:1-type crystalline phase, H2adsorption capacity, and C=O hydrogenation activity of HMF all exhibited a volcano-shaped trend with calcination temperature. Under the conditions of 100 °C and 2.5 MPa H2, Ni-PS-800 enabled HMF hydrogenation with a conversion of 90% and a selectivity of 84% to 2,5-dihydroxymethylfuran (DHMF), in which the catalyst exhibited good stability during five consecutive HMF hydrogenation cycles. The enhanced catalytic performance of Ni-PS-800 is attributed to its high 2:1-type phase fraction, which promotes a pronounced hydrogen-spillover effect and significantly enhances the intrinsic activity for C=O hydrogenation.
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CHINESE JOURNAL OF CHEMICAL ENGINEERING
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2026
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IF 3.5
Yongzhi Xiong,Yihan Wang,Junfang Zhou,Yilin Zhang,Chenge Li,Qi Liu,Yuxin Huang,Linfeng Li,Changzhou Chen,Kui Wang
Ni 3 S 2 -La 2 O 3 heterojunction on sulfur-doped carbon is fabricated. • It achieves 99.05% HMF conversion and 96.62% FDCA selectivity. • Heterojunction boosts charge transfer and lowers reaction energy barrier. • The catalyst reconstructs into Ni(OH) 2 /La 2 O 3 as the true active phase. Herein, we report a ball milling pyrolysis route to prepare highly dispersed Ni 3 S 2 /La 2 O 3 heterostructure nanoparticles immobilized on sulfur-doped carbon (Ni 3 S 2 /La 2 O 3 @SC) for the electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF). Structural characterizations combined with theoretical calculations confirm that the formation of the La 2 O 3 /Ni 3 S 2 heterojunction interface modulates the electronic structure of Ni active sites, thereby enhancing HMFOR performance. Electrochemical performance evaluation shows that Ni 3 S 2 /La 2 O 3 @SC achieves a current density of 100 mA·cm -2 at a potential of 1.697 V vs. RHE, while exhibiting enhanced kinetics for HMF oxidation. I n- situ electrochemical impedance spectroscopy (EIS) further reveals that interfacial charge transfer effectively suppresses the competing oxygen evolution reaction (OER) and promotes HMF oxidation. Through reaction monitoring by high-performance liquid chromatography (HPLC), it is demonstrated that HMF is predominantly converted to 2,5-furandicarboxylic acid (FDCA) via the HMFCA pathway. Under a constant current density of 100 mA·cm -2 , Ni 3 S 2 /La 2 O 3 @SC achieves a HMF conversion of 99.05%, an FDCA selectivity of 96.62%, and a Faradaic efficiency of 82.60%. Density functional theory (DFT) calculations further reveal that the formation of the La 2 O 3 /Ni(OH) 2 heterojunction interface not only suppresses the over-adsorption of HMF on Ni–OH sites and lowers the reaction energy barrier for the critical FDCA desorption step in HMFOR, but also enhances charge transfer between reactants and active sites, thereby facilitating the cleavage of key α-C–H and –O–H bonds during HMFOR. The above studies demonstrate the critical role of interfacial charge transfer in modulating the oxidative activity of Ni–OH active sites and enabling efficient HMFOR. Download: Download high-res image (373KB) Download: Download full-size image
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Research
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2025
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IF 10.7
Yongzhi Xiong,Mengyuan Qiu,Yihan Wang,Qi Liu,Dong Ouyang,Yajun Liu,Changzhou Chen,Jianchun Jiang,Mengmeng Fan,Kui Wang
Efficient utilization of renewable biomass resources is one of the feasible approaches to address the massive consumption of fossil fuels accompanying severe resource crises and environmental pollution. Currently, 2,5-furandicarboxylic acid derived from the oxidation of biomass-based 5-hydroxymethylfurfural (HMF) is a valuable chemical as the alternative to the fossil resource-derived terephthalic acid. However, the development of high-performance and low-cost Cu-based electrocatalysts for the efficient HMF oxidation reaction (HMFOR) remains an enormous challenge. Guided by our theoretical prediction, we proposed a coordination-pyrolysis strategy to fabricate highly dispersed copper sulfide (CuS) nanosheets supported on N-doped porous carbon precatalyst (CuS@NC). The covalent S species trigger the deep reconstruction of CuS nanosheets, and the in situ generated SO 4 2− not only promotes the formation of Cu 2+δ species but also facilitates the cleavage of α–C–H and –O–H bonds in HMF. The optimized CuS@NC achieved a high current density of 335 mA cm −2 at 1.50 V vs. reversible hydrogen electrode, representing a remarkable 628% enhancement over the control catalyst. This study integrates theoretical predictions with experimental investigations to systematically elucidate how S species promote the deep reconstruction of CuS nanosheets to enhance the HMFOR performance and proposes a scalable strategy for preparing ultra-uniform transition metal sulfide precatalysts.
研究领域:
电催化
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材料化学
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可再生能源
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生物质转化
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纳米材料
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PubMed
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
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2025
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IF 5.1
Zhiyong Li,Da Gao,Xiaoge Li,Dingqiang Lu,Jingjing Meng,Kai Guo
Since little attention has been paid to the dual biobased epoxy resin monomers, a novel monomer (ResCMF) from resveratrol and 5-hydroxymethylfurfural was designed for the biobased network fabrication with diaminodiphenyl disulphide (AFD) as a hardener. Comprehensive behaviors of the solvent-free cured networks were investigated. In contrast to the epoxide-amine polymerization in DGEBA/AFD, an additional amine-catalyzed self-polycondensation of ResCMF also occurred during ResCMF/AFD formation. According to the activation energy estimation of the epoxide-amine reaction, the 44AFD hardener is more reactive than the 22AFD. For ResCMF/AFD, the initial epoxide-amine polymerization allowed the network with a moderate T g of about 107.2/109.3 °C, while the self-polycondensation showed high T g values at 194.6 /188.6 °C. Moreover, ResCMF/22AFD outperformed ResCMF/44AFD in terms of storage modulus (4.55 > 3.21 GPa), larger than that of the DGEBA/AFD. It demonstrated outstanding tensile strength (85.1 ± 3.5 MPa) and high flexural strength (118.4 ± 18.9 MPa) as well. Meanwhile, comparable impact and lap shear strengths were observed for all networks. Interestingly, high-performance shape-memory ResCMF/AFD at 150 °C enabled the sustainable reprocessing. Furthermore, in general, the thermosets showed good solvent resistance. Nonetheless, the sustainable post-treatment via DMF-induced solvolysis enables ResCMF/AFD degradation. As a result, the dual-cured ResCMF/AFD networks provide good overall performance for their applications in the future.
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
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2016
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IF 4.179
Fan Wang,Ziliang Yuan,Bing Liu,Shaohua Chen,Zehui Zhang
In this study, a new ruthenium catalyst was used for the oxidation of biomass derived 5-hydroxymethylfurfural (HMF) under mild conditions, which was prepared by the exchange of Ru 3+ with H + in the structure of the zirconium phosphate (ZrP). The as-prepared ZrP–Ru catalyst showed high catalytic activity towards the oxidation of HMF, affording 100% of HMF conversion at 130 °C after 12 h under atmospheric oxygen pressure. 2,5-Furandicarboxylic acid (FDCA) and 2,5-diformylfuran (DFF) were detected to be the major oxidation products.
研究领域:
化学工程
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催化科学
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高影响因子
FUEL
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2020
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IF 5.578
Chaoxin Yang,Xiao Li,Zhenzhou Zhang,Bohan Lv,Jiachun Li,Zhenjian Liu,Wanzhen Zhu,Furong Tao,Guangqiang Lv,Yongxing Yang
The oxidation of 5-hydroxylmethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a sustainable and promising method for the preparation of bio-derived aromatic polyesters . Nitrogen doped carbon material is an effective catalyst support in preparing supported nanoparticle metal catalysts in heterogeneous reactions . In this work, by pyrolysis of bio-waste carbon material, pomelo peel, under 800 °C flowing NH 3 , high nitrogen (up to 11.4 wt%) doped porous carbon material (NC) was facilely obtained. Pt nanoparticles (NPs) can be uniformly dispersed on NC surface and stabilized by the doped nitrogen dopant . Supported Pt NPs by NC-800 (Pt/NC-800) was proved to be an efficient catalyst in aerobic oxidation of HMF into FDCA. Control experiments show that the oxidation of 5-hydrox-ymethyl-2-furancarboxylic acid (HMFCA) to 5-formyl-2-furancarboxylic acid (FFCA) by supported Pt NPs was the key step to determine the oxidation rate of HMF to FDCA. With controlled experiment results and previous reports, a catalytic mechanism involving water, molecular O 2 , hydroxyl ions and Pt NPs was given and explained well of the phenomenon of high HMFCA concentration accumulation during reaction.
研究领域:
化学工程
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催化材料
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高影响因子
APPLIED CATALYSIS A-GENERAL
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2018
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IF 4.521
Zhi Cao,Ming Li,Yong Chen,Tao Shen,Chenglun Tang,Chenjie Zhu,Hanjie Ying
The widely available reagent ethylenediaminetetraacetic acid (EDTA) was used as a temperature-responsive catalyst to produce 5-hydroxymethylfurfural (HMF) from fructose. Using this catalyst, a remarkable HMF yield of 89 ± 3% was achieved in a water-MIBK biphasic system containing polyvinylpyrrolidone (PVP) and 2-butanol. The pH of the reaction system based on EDTA as a catalyst was shown to be temperature-responsive. Moreover, the EDTA catalyst could be recycled simply by cooling the reaction liquid to room temperature due to its temperature-dependent solubility in water. A slight decrease in the yield of HMF (from 89 ± 3 to 81 ± 2%) was observed after EDTA repeated use for five cycles, and a yield of 88 ± 2% was achieved again after purification of the recycled EDTA via recrystallization with NaOH/HCl. The FTIR spectrum of recycled EDTA was almost the same as that of fresh catalyst, and TG analysis showed the decomposition temperature of EDTA is about 260 °C. Furthermore, a leaching test revealed that only 4.3 ± 0.2% of the initial EDTA was lost after five-time reuse.
研究领域:
化学工程
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催化化学
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高影响因子
JOURNAL OF RARE EARTHS
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2025
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IF 7.2
Hao Pan,Zhen Yan,Huihui Cao,Yifei Ye,Jing Zhao,Siyuan Qu,Guangtong Hai,Xiubing Huang
The valorization of 5-hydroxymethylfurfural (HMF) offers a sustainable pathway to address escalating global energy demands, making the design of efficient electrocatalysts for HMF oxidation reaction (HMFOR) a critical research priority. In this study, we synergistically integrated cationic defect engineering and Ce doping to optimize layered double hydroxides (i.e., NiAl-LDHs) for efficient HMFOR. The experimental results show that the coexistence of Ce species and cationic defects synergistically modulates the electronic structure of Ni species, maximizing the exposure of active Ni sites while enhancing electrical conductivity. Furthermore, the introduction of Al 3+ vacancies and Ce 3+ /Ce 4+ redox pairs promotes the formation of high-valent Ni 3+ active species. This dual modification strategy significantly enhances HMFOR performance, with NiAlCe(3%)-LDH-E achieving benchmark metrics at 1.45 V RHE :100% HMF conversion, nearly 100% 2,5-furandicarboxylic acid yield, and nearly 99% Faradaic efficiency. Density functional theory (DFT) calculations validate that cationic defects and Ce doping cooperatively optimize HMF adsorption at active surface centers and reduce the energy barrier for the rate-determining *HMF dehydrogenation to *HMF-to-5-hydroxymethyl-2-furancarboxylic acid (*HMFCA) step, providing atomic-level insights into the enhanced catalytic mechanism.
研究领域:
电催化
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材料科学
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可持续能源
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绿色化学
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密度泛函理论
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DOI
高影响因子
Small
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2024
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IF 13
Ming Li,Haixin Sun,Chen Wang,Yongzhuang Liu,Qinqin Xia,Juan Meng,Haipeng Yu,Shuo Dou
The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) represents an environmentally friendly approach to generate high-value-added chemicals from biomass. The successful electrochemical transformation of HMF during the oxidation reaction (HMFOR) necessitates an ideal adsorption interaction between HMF and OH − on the electrode surface. Yet, catalysts with a singular active site offer limited flexibility in managing the competitive adsorption of HMF and OH − . To this end, different active sites are customized in this work to construct a P and N co-doped porous carbon that wrapped Co 3 O 4 (Co 3 O 4 @PNC). Co-doping with these two heteroatoms generates C 3 P = O and pyrrolic N as adsorption sites to better balance the adsorption of HMF and OH − , respectively, rather than promoting competition between the HMF and OH − on a single active site. With this design strategy, Co 3 O 4 @PNC demonstrates significant HMFOR activity, the conversion rate of HMF surpassed 99% with a 2,5-furandicarboxylic acid (FDCA) yield exceeding 95% after 2 h of electrolysis. Furthermore, it shows universal applicability in the electrooxidation of other alcohol/aldehyde substrates, yielding efficiencies of 90–99%. This work not only provides guidance for advanced electrocatalysts design toward alcohol/aldehyde oxidation but also offers insights into the utilization of biomass-derived platform chemicals.
研究领域:
催化材料科学
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电化学工程
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生物质转化
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PubMed
高影响因子
危险品化学品经营许可证（带存储）