CHINESE JOURNAL OF POLYMER SCIENCE
·
2020
·Vol. 38
·期 10
·1082-1091
·
IF 3.154
Wang Jing-Gang,Zhang Xiao-Qin,Shen Ang,Zhu Jin,Song Ping-An,Wang Hao,Liu Xiao-Qing
In order to explore new substitutes for 2,5-furandicarboxylic acid (FDCA) or poly(ethylene 2,5-furandicarboxylate) (PEF) and try to develop more ideal bio-based polyesters, several thiophene-aromatic polyesters (PETH, PPTH, PBTH, and PHTH) were synthesized from dimethyl thiophene-2,5-dicarboxylate (DMTD) and different diols, including ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. The chemical structures of obtained polyesters were confirmed by nuclear magnetic resonance spectroscopy ( 1 H-NMR and 13 C-NMR). Determined by GPC measurement, their average molecular weight ( M w ) varied from 5.22 × 10 4 g/mol to 7.94 × 10 4 g/mol with the molar-mass dispersity of 1.50–2.00. Based on the DSC and TGA results, the synthesized polyesters PETH, PPTH, and PBTH displayed comparable or even better thermal properties when compared with their FDCA-based analogues. From PETH to PHTH, their T g varied from 64.6 °C to −1 ×C while T 5% ranged from 409 °C to 380 °C in nitrogen atmosphere. PETH showed elongation at break as high as 378%, tensile strength of 67 MPa, and tensile modulus of 1800 MPa. Meanwhile, the CO 2 and O 2 barrier of PETH was 12.0 and 6.6 folds higher than those of PET, respectively, and similar to those of PEF. Considering the overall properties, the synthesized thiophene-aromatic polyesters, especially PETH, showed great potential to be used as an excellent bio-based packaging material in the future.
研究领域:
材料科学
·
生物基材料
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高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2025
·
IF 6.2
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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高影响因子
GREEN CHEMISTRY
·
2022
·Vol. 24
·期 22
·8840-8852
·
IF 11.034
Zongyang Liu,Yuan Tan,Jie Li,Xiuli Li,Yan Xiao,Juan Su,Xingkun Chen,Botao Qiao,Yunjie Ding
Aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a promising alternative route to produce renewable biodegradable plastics, which has stimulated intense interest in recent years. Supported gold catalysts have shown great potential for this reaction, but the selectivity and stability need to be improved. In addition, the requirement for base additives makes the process less effective and sustainable. Herein, highly active and selective Au–Ag bimetallic nanoclusters supported on MgAl-hydrotalcite (HT) were developed for HMF oxidation to FDCA under base-free reaction conditions using molecular oxygen as the oxidant. The presence of small amounts of Ag (0.034–0.065 wt%) in Au25 clusters greatly enhanced the catalytic reaction rates and selectivity for HMF tandem oxidative steps, leading to both high conversion of HMF (>97%) and high yield of FDCA (>95%). Besides, the catalyst stability was also enhanced by the addition of Ag. The characterization results suggested that the substitution of Ag atoms modified the electronic structure of Au while likely maintaining the primary geometry. Thus, a significant synergistic effect could be observed over trace Ag modified Au–Ag bimetallic nanoclusters. The present work provides new insight into the alloying effect, and helps understand highly efficient Au-based catalysts for aerobic oxidation of biomass derived molecules under base-free conditions.
研究领域:
催化化学
·
可再生资源化学
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高影响因子
NEW JOURNAL OF CHEMISTRY
·
2026
·
IF 2.6
Rui Zhang,Shimin Li,Jiale Chen,Jiantao Li,Jian Xiong,Zhihao Yu,Xuebin Lu
A template-assisted approach was employed to synthesize a MOF-on-MOF derived catalyst for the selective oxidation of 5-hydroxymethylfurfural (5-HMF) to produce 2,5-furandicarboxylic acid (FDCA). Characterization revealed that the catalyst forms a cobalt–manganese metal oxide composite phase with a hierarchical porous structure and uniformly distributed Co/Mn active sites. The oxygen vacancies work together with the Lewis acid sites to gradually oxidize the hydroxyl and aldehyde groups in 5-HMF. In the context of reaction conditions that have been identified as optimal (140 °C, 6 h, 50 mg catalyst, 5.88 mol L−1 H2O2), the yield of FDCA was 87.55%, accompanied by 5-HMF conversion rate of 98.66%. The catalyst exhibited exceptional cycling stability, sustaining an FDCA yield exceeding 75% across five cycles. Mechanism studies indicate that the Co–Mn bimetallic synergistic effect optimizes the reaction pathway through electron transfer and oxygen species activation, while the microporous structure prolongs the residence time of intermediates through confinement effect, promoting multi-step oxidation. Compared with the single-metal MOFs derived catalysts, this catalyst has significantly improved adsorption performance and oxidation efficiency, providing an efficient solution for the green synthesis of the bio-based polyester monomer FDCA.
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CATALYSIS LETTERS
·
2026
·Vol. 156
·期 6
·167
·
IF 2.5
Cao Dongyu,Gao Haitao,Wang Tianyi,Chen Jinbo
Developing efficient and stable electrocatalysts is key to converting 5-hydroxymethylfurfural (HMF) into the value-added product 2,5-furandicarboxylic acid (FDCA). Herein, a three-dimensional porous nanosheet-structured nickel-molybdenum-copper (NiMoCu) ternary catalyst was constructed on nickel foam via a two-step electrodeposition strategy coupled with alkaline heat treatment. Characterization (XRD, Raman, TEM, XPS) revealed the homogeneous integration of Ni, Mo, and Cu species at the nanoscale, forming multiple heterointerfaces (MoO 3 –CuO/NiOOH). Meanwhile, Cu incorporation refined the MoO 3 crystallite size to 8.2 nm and promoted the in situ formation of amorphous NiOOH containing Ni³⁺ species. Furthermore, the interfacial electron transfer effect optimized charge transport pathways, thereby promoting an efficient HMFOR process. At 1.47 V vs. RHE, this catalyst showed record HMF electrooxidation performance. The HMF conversion was 99%, FDCA selectivity was near 100%, FDCA yield was 98%, and Faradaic efficiency was 98%. After four cycles in a row, the yield dropped by less than 2%. The excellent performance of the NiMoCu catalyst comes from the synergy of its three metals. Ni³⁺ acts as the active center and drives the reaction. Mo 6+ keeps the Ni³⁺ state stable and speeds up charge movement. Cu stops the side oxygen evolution reaction (OER). The OER contribution is under 2%. This work offers a new way to design efficient and stable catalysts for the electrocatalytic conversion of HMF, a key biomass platform compound. Graphical The alternative text for this image may have been generated using AI.
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高影响因子
EUROPEAN POLYMER JOURNAL
·
2018
·
IF 3.741
Jinggang Wang,Xiaoqing Liu,Zhen Jia,Liyuan Sun,Jin Zhu
The bio-based polyester demonstrating great potential to be used as engineering plastic, poly(1,4-cyclohexanedimethylene furandicarboxylate) (PCF) was synthesized from furandicarboxylic acid (FDCA) and 1,4-cyclohexanedimethanol (CHDM) with different steric conformation. After the chemical structures were identified by nuclear magnetic resonance ( 1 H NMR and 13 C NMR) and molecular weight was determined by gel permeation chromatography (GPC), their crystallization behaviors, thermal and dynamic mechanical properties were investigated by differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA) and dynamic mechanical analysis (DMA). Results showed that PCFs demonstrated very good crystalline properties and the steric configuration of CHDM, i.e. the ratio of cis - to trans -CHDM in PCFs, had significant influences on their properties. The melting temperature of PCF could be as high as 294 °C and its crystallization half-time could be only several seconds. In addition, its mechanical properties and thermal stability were comparable to or better than those of poly(ethylene terephthalate) (PET) or poly(butylene terephthalate) (PBT). Considering the overall performance of PCF, it has great potential to be used as the bio-based polyester engineering plastics.
研究领域:
材料科学
·
化学工程
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DOI
高影响因子
ChemCatChem
·
2025
·
IF 3.9
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.
研究领域:
化学工程
·
材料科学
·
可再生资源
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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
·
材料科学
·
可再生资源与环境
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DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
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
·
催化材料科学
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Han Hu,Jiayi Li,Ying Tian,Shenggan Luo,Jinggang Wang,Wu Bin Ying,Fenglong Li,Chao Chen,Yi-Lei Zhao,Ruoyu Zhang,Jin Zhu
The 2,5-furandicarboxylic acid (FDCA)-based aliphatic–aromatic copolyester is an intensively researched area of bio-based polymers with high gas barrier and mechanical properties. However, the contradiction between the barrier and degradation performance still remains a huge challenge and severely limits their applications. Here, we combine branched neopentyl glycol, hydrophilic diglycolic acid, and FDCA to prepare poly(neopentyl glycol diglycolate/furandicarboxylate) (PNDF) copolyesters. With poor crystallization capability, PNDF40 and 50 (content of NF units) display low modulus (58 vs 108 MPa) but elastomeric behavior. Their tensile broken samples can even rapidly restore the original length, which might be derived from the physical crosslinking networks. It was interesting to find that even when more than 50% of the NF units were replaced by ND units, the PNDF copolyesters still retained high gas barrier. The introduction of diglycolic acid improved the hydrolysis rate, showing potential degradability under environmental conditions. However, enzymatic degradation using Candida antarctica lipase B (CALB) revealed that the branched neopentyl glycol decreased the biodegradation rate when compared with other linear diols. Furthermore, the hydrolytic pathway of PNDF was explored by density functional theory (DFT) calculation. Through Fukui function analysis, we identified the most active sites of PNDF for hydrolysis. Additionally, the calculated energy barrier indicated that hydrolysis of the polymer chain became easier with the increase in the number of ND units. Molecular dynamics (MD) simulations of PNDF–CALB illustrated that Val154 and Gln157 of CALB located at catalytic entrance formed noncovalent interaction with PNDF, which would sterically hinder the carbonyl carbon from reaching an ideal distance for nucleophilic attack and decrease the tendency to enter a pre-reaction state.
研究领域:
材料科学
·
环境科学
·
计算化学
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DOI
高影响因子
Journal of the American Chemical Society
·
2026
·Vol. 148
·期 30
·31794-31805
·
IF 16.6
Zhao Xiaomeng,Sun Jianhui,Bai Linlu,Bai Fuquan,Yang Meilin,Qin Wei,Wang Zhiwei,Yan Xudong,Yin Haochun,Lang Kai,Chen Yuexing,Tang Junwang,Jing Liqiang
Solar-driven biomass valorization is pivotal for defossilizing
the chemical industry. The oxidation of abundant, low-cost 5-hydroxymethylfurfural
(HMF) to 2,5-furandicarboxylic acid (FDCA)─a key monomer for
next-generation bioplastics─is a long-sought goal yet hampered
by sluggish kinetics, poor selectivity, and alkaline dependency. Here,
spatially decoupled catalytic sites are engineered on two-dimensional
carbon nitride (CN): covalently grafted cyanamide (CA) motifs at the
edges and π–π stacked J-type nickel phthalocyanine
(NiPc) dimers on the planes. This design features spatiotemporally
cascaded charge transfer and dual-site catalysis, achieving 54- and
160-fold enhancements in the HMF conversion rate and H 2 evolution rate, respectively, versus pristine CN, during HMF reforming
in pure water. The FDCA production rate reaches 2.14 mmol g –1 h –1 with 98.2% selectivity, outperforming benchmark
systems. Fundamentally, CA motifs steer an ultrafast hole-initiated
selective HMF oxidation with a hole transfer rate of 2.4 × 10 10 s –1 (an order of magnitude faster than
CN). The resulting long-lived electrons are extracted by the bottom-layer
NiPc and transferred via its single Ni atom to the top-layer single
Ni atom for proton reduction, with an electron transfer rate of 7.4
× 10 4 s –1 . The asymmetric charge
kinetics suppresses charge recombination, yielding a charge transfer
efficiency of 98.9%.
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DOI
PubMed
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 21
·15930-15939
·
IF 3.84
Jun Deng,Xiaoqing Liu,Chao Li,Yanhua Jiang,Jin Zhu
A bio-based epoxy monomer, diglycidyl ester of 2,5-furandicarboxylic acid (DGF) was synthesized for the first time from the renewable 2,5-furandicarboxylic acid (FDCA). For comparison study, its petroleum-based counterpart, diglycidyl ester of terephthalic acid (DGT) was also prepared. Their chemical structures were confirmed in detail by 1H NMR, 13C NMR and FT-IR before they were cured by methylhexahydrophthalic anhydride (MHHPA) and poly(propylene glycol)bis(2-aminopropyl ether) (D230), respectively. The curing behaviors were investigated using differential scanning calorimetry (DSC). The thermal mechanical properties and thermal stabilities of the cured resins were evaluated using dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). Results showed that DGF displayed higher curing activity, elevated glass transition temperature and similar mechanical properties compared with those of the cured DGT. This study indicated that FDCA had a huge potential to replace the petroleum-based terephthalic acid in the synthesis of epoxy resins with satisfactory performance.
研究领域:
材料科学
·
化学工程
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高影响因子
危险品化学品经营许可证（带存储）