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ACS Sustainable Chemistry & Engineering · 2016 · IF 5.267

Biocatalytic Upgrading of 5-Hydroxymethylfurfural (HMF) with Levulinic Acid to HMF Levulinate in Biomass-Derived Solvents

Ye-Zhi Qin,Min-Hua Zong,Wen-Yong Lou,Ning Li

Valorization of biomass-based platform chemicals into high value-added products has attracted increasing attention recently. In this work, upgrading of 5-hydroxymethylfurfual (HMF) and levulinic acid, two important biomass-based platform chemicals, to HMF levulinate via a green and efficient enzymatic approach was reported. Novozym 435 was found to be the best biocatalyst for the enzymatic esterification. The enzymatic esterification progressed smoothly in t-butanol, 2-methyl-2-butanol, and cyclopentyl methyl ether as well as in the ecofriendly biomass-derived 2-methyltetrahydrofuran (2-MeTHF), while no enzymatic reaction occurred in deep eutectic solvents. When HMF concentration was up to 500 mM, a good conversion of 72% was achieved in 2-MeTHF. The reaction temperature exerted a significant effect on the enzymatic esterification. When the reaction temperature is below 40 °C, high HMF conversions (>85%) were obtained. Besides, significant inactivation of the enzyme was observed at more than 50 °C, resulting in poor conversions.

CAS / MDL: 5614-37-9
研究领域: 生物化学 · 可再生资源工程
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ChemCatChem · 2025 · IF 3.9

Electrosynthesis of Co-Doped Cu Mesh Catalyst for HMF Oxidation Reaction

Pengwei Deng,Haoran Wu,Huayu Wei,Zixu Yang,Jing Xu,Minghui Zhu

Graphical A modified synthesis method on Cu mesh simplifies and enhances the catalyst preparation process and efficiency at a much lower cost. The synergistic interplay between Co and Cu species is further investigated during the 5-hydroxymethylfurfural oxidation reaction. The Co-doped Cu mesh catalyst's scalability, cost-effectiveness, and robust performance underscore its potential for industrial applications in 5-hydroxymethylfurfural electrooxidation. The growing demand for sustainable alternatives to fossil-derived chemicals has spurred significant interest in biomass valorization, with 5-hydroxymethylfurfural (HMF) emerging as a key platform molecule. In this study, an electrochemical synthesis strategy was employed to synthesize a bimetallic Co-doped Cu mesh catalyst for the HMF oxidation reaction. It exhibited remarkable electrooxidation activity during a 3-h reaction at 1.6 V versus RHE with 83.2% HMF conversion, 99.4% 2,5-furandicarboxylic acid (FDCA) selectivity, and 87.7% Faraday efficiency. X-ray diffraction, in situ surface-enhanced Raman spectroscopy, and X-ray photoelectron spectroscopy revealed that the modified Cu mesh catalyst introduced more Co 3 O 4 species. Additionally, in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy elucidated that Cu species on the Co-doped Cu mesh can adsorb *OH and couple with organic molecules during the reaction process. Cu─Co dual active sites enhance the selective electrochemical oxidation of HMF toward FDCA.

CAS / MDL: 10026-22-9 67-47-0
研究领域: 化学工程 · 材料科学 · 可再生资源
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CATALYSIS LETTERS · 2025 ·Vol. 155 ·期 2 ·1-18 · IF 2.4

Synthesis of UiO–66–NH2(Ti/Zr) and its Catalytic Conversion of Cellulose to 5-HMF

Xu Lingling,Pan Xiaomei,Gao Lijing,Wei Ruiping,Li Jihang,Wen Xiu,Li Yuanzhuang,Xiao Guomin

UiO–66–NH 2 (Ti/Zr) modified by Ti metal oxide (TiO 2 ) was used to catalyze the hydrolysis of cellulose to prepare 5-HMF. Under the optimal reaction conditions of H 2 O(NaCl)/THF(1/4 mL), 190 °C, 2 h and 50 mg UNT-3(Ti/Zr) (TiO 2 and UiO–66–NH 2 with mass of 1.5 and 0.1 g, respectively), the yield of 5-hydroxymethylfurfural reached 59.88%. UiO–66–NH 2 (Ti/Zr) nanocomposites with different mass ratios were successfully prepared by simple solvent evaporation method. SEM and TEM have shown that the modified UiO–66–NH 2 (Ti/Zr) are wrapped into sphere by TiO 2 densely attached to the surface of UiO–66–NH 2 , which provides favorable conditions for the uniform dispersion of TiO 2 and coordination of the Lewis acidic site of UiO–66–NH 2 . NH 3 –TPD results confirmed the existence of super-strong, strong, middle and weak acid sites in UiO–66–NH 2 (Ti/Zr), and Py-FTIR confirmed the existence of Brønsted and Lewis acids. After four cycles, the yield of 5-HMF and FUR decreased slightly from 59.88 to 51.89% and 9.11 to 7.66%, respectively, and the yield of 5-HMF could still remain above 50%. The results showed that the modified composite treatment of TiO 2 with rich Lewis acid/base and UiO–66–NH 2 could provide a certain idea for the extensive application of biomass research in the future. Graphic

研究领域: 材料科学 · 催化化学 · 生物质能研究
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JOURNAL OF MEMBRANE SCIENCE · 2025 · IF 9

Toward tailored anion exchange membranes for high-performance electrocatalytic oxidation of HMF to FDCA

Xuehui Ge,Jun Qian,Zhen Zhu,Yafei Cheng,Lei Yuan,Jinjie Jia,Xiaolei Liu,Hongwei Zhang,Xiaocheng Lin

Membrane separator that is highly ionic conductive and alkaline stable is essential for the efficient, scalable electrocatalytic oxidation of HMF to FDCA, a key process for sustainable development. Drawing inspiration from the microstructural design of Nafion, we developed a series of side-chain imidazolium-functionalized anion exchange membranes (AEMs), employing the chemically stable polyethersulfone (PES) as the base polymer. Functionalization of PES side chains with chloromethyl groups, followed by C2-substituted imidazolium modification, enabled precise tuning of the membrane's physicochemical properties and structural characteristics. This tailored approach yielded an optimized DIM-PES-1.0 AEM exhibiting complete HMF conversion, with 94.0 % selectivity for FDCA and 94.1 % Faradaic efficiency, outperforming the commercial Fumasep FAA-3-PK-130 AEM, which achieved only 85.5 % FDCA selectivity under similar conditions. Notably, the DIM-PES-1.0 AEM demonstrated high alkaline stability, substantially retaining its electrocatalytic activity across 15 cycles, in contrast to the rapid degradation observed in FAA-3-PK-130 AEM after only three cycles. Our findings showcase a scalable, efficient strategy for producing high-performance AEMs under mild conditions, highlighting their potential for advancing sustainable electrocatalytic processes.

CAS / MDL: 1739-84-0
研究领域: 化学工程 · 可持续发展 · 电催化
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INDUSTRIAL CROPS AND PRODUCTS · 2025 · IF 6.2

Activating efficient HMF electro-oxidation activity of biochar-loaded MoS2 by Co-modified

Yongzhi Xiong,Wei Zhao,Changzhou Chen,Mengyuan Qiu,Yingrui Dong,Yajun Liu,Jianchun Jiang,Mengmeng Fan,Kui Wang

In this study, a novel Co-modified MoS 2 loaded spherical biochar (Co-MoS 2 @BC) derived from renewable biomass was synthesized as an efficient anodic HMFOR electrocatalyst. In the HMFOR process, the Co-MoS 2 @BC required a potential of only 1.426 V for the current density of 100 mA/cm 2 , significantly outperforming that of the MoS 2 loaded on spherical biochar (MoS 2 @BC) and the Co nanoparticles loaded on spherical biochar (Co@BC). Furthermore, the HMF conversion ratio reached 99.6 %, FDCA selectivity was 99.7 %, and Faradaic efficiency was 99.3 %. The Mechanistic studies reveal that the modified-Co on the MoS 2 modulated the electronic structure of Co-MoS 2 @BC, which not only enhanced the interaction between Co-MoS 2 @BC and the electrolyte, thereby facilitating the evolution of the catalysts toward highly active species, but also improved the adsorption of HMF and the H + transfer e - coupling step during the HMFOR process.

研究领域: 材料科学 · 电化学 · 可再生能源
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BIOMASS & BIOENERGY · 2024 · IF 5.8

Selective HMF synthesis from glucose via microwave-assisted metal chloride catalysis

Jiawei Cai,Chao Xu,Weijian Shi,Shuping Wu

Microwave-assisted heating technology is considered to be a novel catalytic method. In this study, the microwave method was combined with the low-toxic metal chloride catalyst AlCl 3 and the green solvent GVL, to directly catalyze the conversion of glucose to HMF with the assistance of the microwave. Under the optimized reaction conditions, the ratio of water to organic phase GVL was 4:6 as the solvent, and the yield of HMF was 74.04 % when the mixture was reacted for 10 min under 220 W microwave power. Using H 2 O and GVL as solvents, the obtained reaction solution will be divided into an aqueous layer and an organic layer. The catalyst AlCl 3 mainly exists in the aqueous layer, and the product HMF is mainly distributed in the organic layer. This facilitates the separation of HMF and the recycling of the catalyst. This work highlights an efficient and environmentally friendly reaction system, which is expected to provide ideas for the preparation of HMF on an industrial scale.

CAS / MDL: 67-47-0
研究领域: 化学工程 · 环境科学
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Molecular Catalysis · 2024 · IF 3.9

Photocatalytic selective oxidation of HMF to DFF based on hollow CdS QDs/MIL-101 composites under visible light

Yuwei Liang,Chunling Hu,Peng Chen,Qi Li,Jianning Wu,Zhiyong Liu,Jichang Liu,Yanlong Tai

5-hydroxymethylfurfural (HMF) can catalyte into 2,5-diformylfuran (DFF) which had received much attention as a potential biomass resource. Here, we used a simple and effective method to construct hollow CdS quantum dot (CdS QDs)/MIL-101 heterostructures with high contact area and multiple active sites. The structure of heterostructures could improve photocatalytic activity by charge transfer, photogenerated carrier separation and the multiple refractions of light supported within the hollow-structured CdS QDs. The detailed catalytic mechanism was illustrated by trap agent experiments and electron paramagnetic resonance (EPR) spectroscopy, in which superoxide radicals (·O 2 - ) play a decisive role in the catalytic oxidation of HMF to DFF. Furthermore, the large specific surface area of MIL-101 adsorbs O 2 from the reaction system thereby accelerating the ·O 2 - formation process. Under environmental conditions, 70 % CdS QDs/MIL-101 exhibited optimal catalytic performance. Comparing with pure CdS QDs, the photocurrent enhances 1.8 times, HMF conversion is 1.5 times and DFF selectivity is 1.2 times. This work provide a useful way to improve the conversion of biomass by Z-heterostructures under ambient conditions.

研究领域: 化学工程 · 材料科学 · 环境科学
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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Oxygen defect engineering in Pt/CeO2 catalyst for promoted selective oxidation of HMF to FDCA

Fuyuan Qi,Weiping Yang,Lan-Lan Lou,Shuangxi Liu,Kai Yu

Oxygen vacancies play an important role in the oxidation of biomass-derived alcohols and aldehydes using ceria-based catalysts. In this study, a highly oxygen vacancy-defective Pt/H-CeO 2 catalyst was synthesized by a straightforward strategy that involved the control of the addition of ascorbic acid and nitric acid. The addition of ascorbic acid, which acted as a pore-forming agent, promoted the hydrolysis, crystallization, and subsequent growth of Ce precursor salt, resulting in the synthesis of H-CeO 2 with abundant oxygen vacancy defects and a porous thin sheet-like morphology. However, the addition of nitric acid significantly inhibited the generation of oxygen vacancy defects. The obtained H-CeO 2 exhibited significantly increased oxygen vacancy content, active oxygen species, and specific surface area compared with CeO 2 with lower oxygen vacancy defects (L-CeO 2 ). These remarkable features led to enhanced catalytic activity of Pt/H-CeO 2 for the oxidation of 5-hydroxymethylfurfural (HMF) compared with Pt/L-CeO 2 . This can be mainly attributed to the enhanced adsorption and activation of O 2 molecules by abundant oxygen vacancies, allowing more active oxygen species to participate in the dehydrogenation of HMF. This work provides an example of oxygen defect engineering for ceria-based catalysts to boost the catalytic selective oxidation performance.

研究领域: 催化化学 · 材料科学
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ChemSusChem · 2021 ·Vol. 15 ·期 13 ·e202101983 · IF 8.928

Crystal Faces-Tailored Oxygen Vacancy in Au/CeO2 Catalysts for Efficient Oxidation of HMF to FDCA

Yanan Wei,Yunlei Zhang,Yao Chen,Fang Wang,Yu Cao,Wen Guan,Xin Li

Graphical Saving face : Catalytic performance of Au/CeO 2 with different exposed CeO 2 crystal faces for oxidation of 5-hydroxymethlfurural to 2,5-furandicarboxylic acid is dependent on the oxygen vacancy (V O ) concentration. Higher V O concentration of Au/rod-CeO 2 (110) is more beneficial for adsorption of oxygen and formation of active oxygen species than Au/cube-CeO 2 (100) and Au/oct-CeO 2 (111). Developing an efficient catalyst to upgrade 5-hydroxymethylfurfural (HMF) to high-value-added downstream chemicals is of great significance in biomass conversion. Nanorod (110)-, nanocube (100)-, and nanooctaheron (111)-CeO 2 -supported Au nanoparticles were prepared to investigate the intrinsic effect of CeO 2 crystal faces on the oxidation of HMF to 2,5-furandicarboxylic acid (FDCA). The experimental results and density functional theory calculation revealed that the concentration of oxygen vacancy (V O ) for exposed specific crystal faces was crucial to the oxygen adsorption ability, and Au/nanorod-CeO 2 with the highest V O concentration promoted the formation of more oxygen active species (superoxide radical) on CeO 2 (110) crystal face than (100) and (111) crystal faces. Besides, the higher V O concentration could provide a strong adsorption ability of HMF, greatly boosting the activation of HMF. Thus, these results led to a superior catalytic activity for HMF oxidation over Au/nanorod-CeO 2 (FDCA yield of 96.5 %). In-situ Fourier-transform (FT)IR spectroscopy uncovered the HMF oxidation pathway, and the possible catalytic mechanism was proposed. The deep insight into the role of regulation for crystal faces provides a basis for the rational design of highly active facets for the oxidation of HMF and related reactions.

CAS / MDL: 3238-40-2 67-47-0
研究领域: 催化化学 · 材料科学 · 生物质转化
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JOURNAL OF HAZARDOUS MATERIALS · 2014 · IF 4.331

Chlorogenic acid increased acrylamide formation through promotion of HMF formation and 3-aminopropionamide deamination

Yun Cai,Zhenhua Zhang,Shanshan Jiang,Miao Yu,Caihuan Huang,Ruixia Qiu,Yueyu Zou,Qirui Zhang,Shiyi Ou,Hua Zhou,Yong Wang,Weibing Bai,Yiqun Li

This research was aimed to investigate why chlorogenic acid, presents at high concentrations in some food raw material, influences acrylamide formation. In the asparagine/glucose Maillard reaction system (pH   =   6.8), addition of chlorogenic acid significantly increased acrylamide formation and inhibited its elimination. In contrast, the quinone derivative of chlorogenic acid decreased acrylamide formation. Three mechanisms may be involved for increasing acrylamide formation by chlorogenic acid. Firstly, it increased the formation of HMF, which acts as a more efficient precursor than glucose to form acrylamide. Secondly, it decreased activation energy for conversion of 3-aminopropionamide (3-APA) to acrylamide (from 173.2 to 136.6   kJ/mol), and enhances deamination from 3-APA. And thirdly, it prevented attack of the produced acrylamide from free radicals by keeping high redox potential during the Maillard reaction.

研究领域: 食品科学 · 化学
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Biomass Conversion and Biorefinery · 2022 · IF 4.05

Porous nitrogen-doped carbons supporting Fe-porphyrins for the highly efficient catalytic oxidation of HMF to HMFCA

Gao De,Han Feng,Waterhouse Geoffrey I. N.,Li Yan,Zhang Lili

A series of FeTPP-N/C-X catalysts were successfully prepared by adsorption of Fe tetraphenylporphine (FeTPP) onto a porous nitrogen-doped carbon (N/C) support using an ultrasonication method. The FeTPP-N/C catalysts were then used for the preparation of 5-hydroxymethyl-2-furan acid (HMFCA) by catalytic oxidation of 5-hydroxymethylfurfural (HMF) at 80 °C. The effects of reaction temperature, NaOH dosage, reaction time, and oxygen pressure on HMF conversion and HMFCA yield were systematically investigated. Under optimized testing conditions, a FeTPP-N/C-1 catalyst prepared using equal masses of FeTPP and N/C delivered a HMF conversion in water of 92.4%, with a selectivity to HMFCA of 97.2% over 6 h at an oxygen pressure of 1.0 MPa. Further, the catalyst showed good stability in five consecutive HMF oxidation tests. Based on the catalytic tests, and detailed catalyst characterization studies before and after reaction, a probable reaction mechanism was proposed for the selective oxidation of HMF to HMFCA by the FeTPP-N/C catalysts. Graphical Abstract A series of FeTPP-N/C catalysts were successfully prepared by the adsorption of iron tetraphenylporphine (FeTPP) onto a porous nitrogen-doped carbon (N/C) support using an ultrasonication method. The FeTPP-N/C catalysts were then used for the catalytic aerobic oxidation of HMF to HMFCA. Under the optimized reaction conditions (temperature 80 °C, reaction time 6 h, O 2 pressure 1 MPa), a high HMF conversion of 92.4% and a remarkable HMFCA selectivity of 97.2% were obtained, suggesting that the developed noble-metal free catalyst has excellent promise for the synthesis of valuable HMFCA from HMF.

CAS / MDL: 13529-17-4 6338-41-6
研究领域: 材料科学 · 催化化学
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MOLECULES · 2025 ·Vol. 30 ·期 8 ·1780 · IF 4.6

Electrocatalytic Oxidation of HMF to FDCA over Multivalent Ruthenium in Neutral Electrolyte

Shiying Yang,Xin Jin,Bin Zhu,Dan Yang,Xiaoyue Wan,Yihu Dai,Chunmei Zhou,Yuguang Jin,Yanhui Yang

5-Hydroxymethylfurfural (HMF) serves as an important bridge connecting biomass resources with fossil fuels. Its downstream product, 2,5-furandicarboxylic acid (FDCA), is a renewable alternative to terephthalic acid (TPA) in the synthesis of various polymer materials. In this study, we successfully synthesized four ruthenium-based catalysts with varying valence states supported on carbon nanotubes (CNTs) and compared the performance of HMF electrooxidation. Among these, the Ru+2.9catalyst demonstrated the highest activity for the electrochemical oxidation of HMF to FDCA in the neutral medium (0.1 M K2SO4). Notably, the FDCA yield reached 90.2% under an applied potential of 0.95 V (vs. Ag/AgCl) after 24 h. Mechanistic analysis revealed that the superior specific capacitance of the Ru+2.9catalyst significantly facilitated the reaction process. This work represents a more cost-effective approach to avoid the need for excessive alkaline additives during catalyst preparation and the HMF oxidation process, and FDCA separated easily after cooling the reaction solution down.

研究领域: 能源化学 · 催化化学 · 生物质转化
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