APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Xiang Li,Wangchuan Zhu,Feng Yue,Huijuan Pang,Chuantao Wang,Danjun Wang,Yuxuan Lu,Chunming Yang
Copper-based compounds exhibit broad prospects in the electrocatalytic oxidation of biomass for sustainable production of high-value-added chemicals due to their passivated oxygen evolution reaction (OER) competitiveness. However, the sluggish reaction kinetics remain the main challenge in constraining their scalable application. Herein, a highly selective electrooxidation of 5-hydroxymethylfurfural (HMF) to 2, 5-furandicarboxylic acid (FDCA) on CuO is achieved via photoinduced surface reconstruction. The experimental results confirmed that the photogenerated hole accumulation on the surface of CuO with matched valence band position can promote the CuOOH active phase generation. Density functional theory (DFT) calculations and the overall relationship between structure and selectivity indicate the CuOOH species can accelerate the spontaneous dehydrogenation process of hydroxyl group . Therefore, the activated CuO electrode under illumination can effectively regulate the conversion of 5-Hydroxymethyl-2-furancarboxylic acid (HMFCA) key intermediates and exhibits accelerated reaction kinetics, FDCA yield increased by 17.79 % compared to dark condition. Additionally, a general enhancement effect on the oxidation of benzyl alcohol and furfuryl alcohol was also revealed. This work introduces photoassistance effect for the first time in HMF oxidation, opening up prospects for the application of photoelectric synergy in biomass value-added conversion and providing insights into the activity mechanism of Cu-based catalysts in organic oxidation.
研究领域:
化学工程
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材料科学
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DOI
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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DOI
高影响因子
Journal of Chemistry
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2018
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IF 1.726
Zou Bin,Chen Xueshan,Xia Jiaojiao,Zhou Cunshan
Conversion of HMF into FDCA was carried out by a simple and green process based on alkaline ionic liquid (IL) modified Pd/C catalyst (Pd/C-OH−). Alkaline ionic liquids were chosen to optimize Pd/C catalyst for special hydrophilicity and hydrophobicity, redox stability, and unique dissolving abilities for polar compounds. The Pd/C-OH− catalyst was successfully prepared and characterized by SEM, XRD, TG, FT-IR, and CO2-TPD technologies. Loading of alkaline ionic liquid on the surface of Pd/C was 2.54 mmol·g−1. The catalyst showed excellent catalytic activity in the HMF oxidation after optimization of reaction temperature, reaction time, catalyst amount, and solvent. Supported alkaline ionic liquid (IL) could be a substitute and promotion for homogeneous base (NaOH). Under optimal reaction conditions, high HMF conversion of 100% and FDCA yield of 82.39% were achieved over Pd/C-OH− catalyst in water at 373 K for 24 h.
研究领域:
催化化学
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绿色化学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2023
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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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DOI
高影响因子
Molecular Catalysis
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2025
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IF 4.9
Rui Zhu,Fang Gao,Xinglong Li
The development of efficient catalysts for the stepwise oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformyl furan (DFF), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), 5-Formyl-2-furancarboxylic acid (FFCA) or 2,5-furandicarboxylic acid (FDCA) is critical for biomass valorization. Herein, we reported a bimetallic Co-Mn catalyst anchored on nitrogen-doped porous carbon, which was used for the oxidation of HMF to FDCA, avoiding the use of high temperature and high-pressure oxygen. High FDCA selectivity (>95 %) was achieved through reaction condition optimization. And HMF→DFF→FFCA→FDCA was considered to be the main reaction pathway during the whole oxidation process. Additionally, the chemical environment of the constituent elements of the used catalyst was analyzed by XPS. TEM revealed that the catalyst retained its porous structure and excellent metal dispersion after the reaction. This structural stability was corroborated by sustained >90 % FDCA selectivity over five consecutive reaction cycles. This work established a dual-metal synergy strategy for multi-step oxidation pathways, offering insights into the design of robust catalysts for biomass-derived platform molecule upgrading.
研究领域:
化学催化
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生物质转化
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材料科学
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DOI
高影响因子
Polymers
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2017
·Vol. 9
·期 9
·305
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IF 3.364
Jinggang Wang,Xiaoqing Liu,Jin Zhu,Yanhua Jiang
Bio-based polyesters derived from 2,5-furandicarboxylic acid (FDCA), including poly (ethylene 2,5-furandicarboxylate) (PEF), poly(propylene 2,5-furandicarboxylate) (PPF), and poly(butylene 2,5-furandicarboxylate) (PBF) have been synthesized and modified with 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO). Copolyesters with increased glass transition temperature, good barrier and better mechanical properties, as well as higher transparency were reported in this work. The chemical structures, composition, and sequence distribution of the copolyesters were determined by1H NMR and13C NMR. The degree of random (R) was close to 1 for all the copolyesters, indicating their random chemical structures. With the introduction of 10% CBDO units, the semi-crystalline PEF and PPF were changed into completely amorphous polyesters and the higher transparency was easily achieved. The glass transition temperature was increased from 87 °C for PEF to 91.1 °C for PETF-18, from 55.5 °C for PPF to 63.5 °C for PPTF-18, and from 39.0 °C for PBF to 43.5 °C for PBTF-18. The barrier properties investigation demonstrated that although the O2and CO2barrier of PEF/PPF/PBF were decreased by the addition of CBDO units, the modified copolyesters still showed good barrier properties.Keywords:2,5-Furandicarboxylic acid (FDCA);poly (ethylene 2,5-furandicarboxylate) (PEF);poly(propylene 2,5-furandicarboxylate) (PPF);poly(butylene 2,5-furandicarboxylate) (PBF);2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO)
研究领域:
材料科学
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化学工程
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DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF ADHESION AND ADHESIVES
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2026
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IF 4
Jiawei Fang,Yu Long,Xingzhen Feng,Yue Zhao,Dawei Zhang,Ligang Zhang,Kaiyuan Qian,Meng Xin,Guohua Fan,Chuncheng Hao
Bio-based FDCA was incorporated into PBS to improve adhesive performance. • Copolyester polyols and reactive PURHMAs were synthesized by tuning monomer ratios. • 30% FDCA delivers 8.20 MPa lap shear strength with high thermal stability. To address the shortcomings of mechanical properties in conventional bio-based adhesives, this study innovatively incorporates bio-based 2,5-furandicarboxylic acid (FDCA), which features a rigid ring structure, into the poly(butylene sebacate) system. By adjusting the monomer ratios, a series of copolyester polyols and reactive polyurethane hot-melt adhesives (PURHMAs) were synthesized. Systematic characterization results indicate that the incorporation of FDCA significantly enhances the mechanical performance of the materials. Specifically, when FDCA accounts for 30% of the total acid component in molar terms, the lap shear strength of PURHMAs on PC substrates reaches 8.20 MPa, representing a notable improvement compared to the unmodified system, while excellent thermal stability is maintained. This research confirms the significant potential of copolymerization modification strategies in developing high-strength, heat-resistant bio-based adhesives.
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2026
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IF 12.5
Wangjie Chu,Shengkai Ke,Kexin Feng,Weizhen Xie,Zecui Sheng,Lu Lin,Xing Tang
Base-regulated ROS strategy enables mild HMF-to-FDCA oxidation. • NaHCO 3 stabilizes ·O 2 − ; NaOH promotes ·O 2 − /·OH synergy. • NaOH system drives O 2 relay: O 2 → ·O 2 − → H 2 O 2 → ·OH for FDCA synthesis. The sustainable conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) via aerobic oxidation is a cornerstone of future biorefinery, yet its practical implementation under mild conditions is constrained by the spin-forbidden activation of triplet O 2 . In this work, we report a base-regulated reactive oxygen species (ROS) strategy that enables efficient HMF oxidation to FDCA at low temperatures (30–60 °C) under ambient oxygen pressure. We find that weak base NaHCO 3 selectively stabilizes ·O 2 − , directing a selective oxidation pathway, whereas strong base NaOH promotes a synergistic ·O 2 − /·OH mechanism that substantially accelerates the overall reaction. Through careful optimization, a 95.8% FDCA yield is obtained under ambient O 2 flow. Kinetic analysis, including reaction order determination and kinetic isotope effect measurements, demonstrates that O 2 activation is the rate-limiting step in the NaOH system, following a relay activation pathway of O 2 → ·O 2 − → H 2 O 2 → ·OH. This work not only elucidates the mechanistic role of bases in regulating ROS during HMF oxidation but also provides a practical and green route for synthesizing FDCA under mild, ambient-pressure conditions, advancing the field of sustainable biomass conversion. This work demonstrates a base-regulated reactive oxygen species (ROS) strategy for the mild oxidation of HMF to FDCA. The weak base NaHCO 3 selectively stabilizes ·O 2 − , directing a selective oxidation pathway, whereas the strong base NaOH promotes synergistic ·O 2 − /·OH participation, substantially accelerating the reaction. Mechanistic studies reveal that O 2 activation follows a relay pathway: O 2 → ·O 2 − → H 2 O 2 → ·OH in the NaOH system. Under ambient oxygen pressure and at 30–60 °C, a 95.8% FDCA yield is achieved, offering a new route for green biomass conversion. Download: Download high-res image (47KB) Download: Download full-size image
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DOI
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
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2022
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IF 4.966
Guoqiang Wang,Yakun Dong,Xingyu Hao,Li Zhang,Xiang Chi
Currently, a growing focus is devoted to the creation and utilization of renewable resources for bio-based polyesters due to the shortage of oil resources. Since 2,5-furandicarboxylic acid (FDCA) has been described as one of the most promising platform compounds, FDCA-based polyesters have been rapidly developed. Poly(decylene terephthalate- co -decylene furandicarboxylate) (PDTFs) in this study were prepared from dimethyl terephthalate (DMT), 1,10-decanediol (DDO) and dimethyl 2,5-furandicarboxylate (DMFD). By using 1 H NMR and 13 C NMR, the polyesters' chemical structure was verified. The thermal properties and the thermal stability of the polyesters were analyzed by Differential Scanning Calorimetry (DSC) and Thermogravimetric analysis (TGA). All polyesters underwent mechanical testing to ascertain their Young's modulus , tensile strength , and elongation at break. All polymers are semi-crystalline materials. The crystal texture of PDTF24 is equivalent to that of poly(decylene terephthalate) (PDT). However, the crystal structures of PDTF48 and PDTF76 are similar to that of poly(decylene furandicarboxylate) (PDF). All polymers exhibit high thermal stability. PDF has the highest tensile strength, probably because the oxygen atom on the furan ring results in stronger intermolecular interactions . When the content of the decylene furandicarboxylate unit reaches 48%, Young's modulus reaches its lowest value (96.6 MPa), but its elongation at break reaches its highest value (1098%) due to the lowest crystallinity .
研究领域:
材料科学
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化学工程
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产品关联
DOI
高影响因子
POLYMER DEGRADATION AND STABILITY
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2023
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IF 5.9
Ruixue Gao,Jinggang Wang,Fei Liu,Hang Dai,Xiaoqin Zhang,Xiaoxing Wang,Yiguo Li,Jin Zhu
As a novel polyester possessing high melting temperature and well crystallization ability, poly(1,4-cyclohexanedimethylene furandicarboxylate) (PCF), produced from bio-based 2,5-furandicarboxylic acid and 1, 4-cyclohexanedimethanol, could be used as promising hard segment to develop new bio-based thermoplastic poly(ether-ester) elastomer (TPEE). Multiblock poly(ether-ester)s based on PCF, with molecular weight ( M n ) of soft segments poly(tetramethylene glycol) (PTMG) ranging from 250 to 2900 g/mol while maintaining the weight fraction at 70%, were synthesized to investigate the effects of soft segments length on microphase structure and thermodynamic properties of copolymers. The results show that the increase in M n of the soft segment promotes the microphase separation of the copolymers. Macroscopically, copolymers have excellent comprehensive properties. T m was promoted from 126.0 to 228.7 °C, and T d,5% was higher than 320 °C. The tensile strength and modulus of resulting copolymers were within the range of 14–26 MPa and 29–53 MPa, respectively, with elongation at break exceeding 550%. The copolymer exhibited elastic recovery ratio of 75.5% at 200% strain when the M n of PTMG unit was 2000 g/mol. This work introduces a new bio-based TPEE and enriches a detailed understanding of the impact of soft segments length on the structural properties of TPEE, which is fundamental to design tailor-made TPEE with desired properties.
研究领域:
材料科学
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聚合物化学
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DOI
高影响因子
JOURNAL OF CATALYSIS
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2018
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IF 6.759
Tianyu Gao,Jing Chen,Wenhao Fang,Qiue Cao,Weiping Su,Franck Dumeignil
Mn-Ce mixed oxides-supported Ru nanoparticles (Ru/Mn X Ce 1 O Y ) with enhanced oxygen mobility and strong metal-support interaction were prepared and applied to the aerobic oxidation of 5 -hydroxymethylfurfural (HMF) to 2,5 -furandicarboxylic acid (FDCA) without addition of any base additives. Oxygen and water were used as green oxidant and solvent, respectively. The catalysts were characterized in depth by XRD, H 2 -TPR, O 2 -TPD, UV–Vis DRS, XPS and TEM, to reveal materials properties from bulk to surface. The influence of Mn/Ce molar ratios in support materials and reaction parameters ( i.e. , HMF/Ru ratio, O 2 pressure, reaction temperature and time) was systematically studied and optimized. The reaction route and rate-determining step for oxidation of HMF to FDCA over the Ru/Mn X Ce 1 O Y catalysts were investigated by kinetic analysis. Well-dispersed metallic Ru nanoparticles with a mean size of 4.4 nm deposited on the support were found essential to activate and oxidize the HMF molecule. The Mn/Ce molar ratio was found to affect not only conversion of HMF but also distribution of products. The Ru/Mn 6 Ce 1 O Y catalyst demonstrated an exceptional yield (≥99%) of FDCA, which corresponds in our conditions to one of the best productivity (5.3 mol FDCA ·mol Ru −1 ·h −1 ) ever reported in literature. The superior activity of the Ru/Mn 6 Ce 1 O Y catalyst was mainly associated with (i) the strong metal-support interaction and (ii) the synergistic effect between manganese and cerium oxides. This catalyst showed the highest surface concentrations in Mn 4+ and Ce 3+ among the series, which, as a consequence, enhanced the availability and mobility of active oxygen species. This catalyst was shown resistant to deactivation during eight recycling uses thanks to a strong metal-support interaction between Ru nanoparticles and the Mn-Ce mixed oxide used as a support.
研究领域:
催化化学
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绿色化学
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材料科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2026
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IF 13.2
Hao-Yue Ma,Jun-Fei Gu,Xing-Chuan Li,Zhan Chen,Qi-Yu Fu,Francis Verpoort,Wen-Jie Mo,Zheng Liu,Cheng Chen,Soon Hyeok Hong,Zongkui Kou
The transition from petroleum-derived chemicals to sustainable alternatives has intensified interest in 2,5-furandicarboxylic acid (FDCA), a biomass-derived monomer for green polyester production. However, many non-noble metal catalysts for converting 5-hydroxymethylfurfural (HMF) to FDCA still require multistep syntheses and/or harsh oxidation conditions. Here, we report a straightforward molten-salt strategy to prepare nitrogen-doped porous carbon–supported cobalt catalysts (Co@N-C-x). Under ambient air at 90 °C in water, the optimized [email protected] catalyst affords complete HMF conversion and > 99 % FDCA yield, with a productivity of ~1.17 mol FDCA mol Co −1 h −1 , and retains 96.5 % yield in an initial 400-fold scale-up test. Mechanistic and kinetic analyses support a sequential pathway of HMF → HMFCA → FFCA → FDCA, with the FFCA-to-FDCA step being kinetically most demanding under the present conditions. Structure–activity analysis, together with atmosphere-dependent experiments, indicates that Co–Nₓ sites serve as the primary catalytic centers, while adjacent defect-rich surface sites (denoted as O₂-activation sites) promote dioxygen activation and facilitate stepwise oxidation. Density functional theory calculations further show that FDCA binds more strongly to the catalyst surface than the intermediates, which can hinder product desorption and contribute to the observed loss of activity upon recycling.
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高影响因子
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