CHEMBIOCHEM
·
2018
·Vol. 19
·期 7
·654-659
·
IF 2.774
Ke-Feng Wang,Chun-lei Liu,Kun-yan Sui,Chen Guo,Chun-Zhao Liu
Graphical Cleaning up catalysis : There is a great need for the eco-efficient and sustainable oxidation of bio-based chemicals by using clean catalysts. In this study, magnetic laccase catalyst with TEMPO as the mediator showed high activity in the oxidation of 5-hydroxymethylfurfural (HMF). Interesting and promising results were obtained, with 90.2 % yield of 2,5-furandicarboxylic acid (FDCA) and complete HMF conversion. 2,5-Furandicarboxylic acid (FDCA) is a bio-based platform chemical for the production of polyethylene furanoate (PEF) and other valuable furanic chemicals. A magnetic laccase catalyst with (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) as the mediator has the remarkable capability of oxidizing 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). Under optimal reaction conditions, a quantitative yield (90.2 %) of FDCA with complete HMF conversion was obtained after 96 h of reaction. More importantly, the magnetic laccase catalyst exhibited good recyclability and stability, maintaining 84.8 % of its original activity following six reuse cycles. This is the first report on the efficient catalytic oxidation of HMF to FDCA by using an immobilized enzyme catalyst.
研究领域:
催化
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生物技术
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绿色化学
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生物基化学品
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Yunlei Zhang,Yu Cao,Changhao Yan,Wenyun Liu,Yao Chen,Wen Guan,Fang Wang,Yiran Liu,Pengwei Huo
Upgrading bioderived 5-hydroxymethylfurfural (HMF) to high value-added bioplastic monomer 2,5-furandicarboxylic acid (FDCA) is a promising route for biomass conversion. Developing an efficient supported metal catalyst and clarifying the structure–activity relationship between the support and active sites is the key to boost FDCA production. Herein, ZrO 2 coated on natural and abundant halloysite nanotubes (HNTs) was synthesized and employed as a support for Au nanoparticles loading. The Au-ZrO x interface active sites were successfully engineered, and the active site amount can be rationally tailored by adjusting the crystal phases of ZrO 2 via changing calcination temperature. A combination study of catalysts surface physicochemical properties and catalytic activity reveals that oxygen vacancies (O v ) play a vital role in enhancing the adsorption of O 2 . Meanwhile, interface active sites facilitate the chemisorption and activation of O 2 molecules, which makes it easier to produce oxygen active species (superoxide radicals). More importantly, in-situ infrared spectroscopy and adsorption experiments also demonstrate that the catalyst with a higher O v concentration not only contributes to a stronger Lewis acid intensity, but also enhances the adsorption capacity of a key intermediate 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), thus leading to an acceleration of the rate-determining step of hydroxyl group oxidation. The highest 99.4 % of FDCA yield can be obtained in 3.0 h. This newly proposed model of interface active sites may shed a light on the design of novel heterogeneous catalysts for the related biomass oxidation reactions.
研究领域:
催化
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材料科学
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化学工程
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生物质转化
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产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 34
·18421-18430
·
IF 12.732
Honglei Wang,Chong Li,Jintao An,Yuan Zhuang,Shengyang Tao
2,5-Furandicarboxylic acid (FDCA), as an important monomer to produce biodegradable polymers, is a hot compound in the field of electrocatalysis. Designing high-activity and low-cost electrocatalysts for the production of high concentration FDCA is an urgent and challenging task. Here, a cactus-like NiCoP nanoplate was prepared as a robust electrocatalyst to enable 5-hydroxymethylfurfural (HMF) oxidation to FDCA at high concentration. In situ Raman spectroelectrochemical analysis investigated the dynamic structural evolution of the NiCoP surface during the electrooxidation of HMF. The substituted Co atoms make the NiOOH active species easier to form on the NiCoP surface than Ni2P at low constant voltage, which promotes the oxidation of HMF into FDCA. The total potential of coupling the cathodic H2 reduction reaction with the anodic HMF oxidation reaction (HMFOR) is only 1.464 V when NiCoP is the electrode material. The design of the flow-through mode reactor optimized the mass transfer process in the reaction, and further improved the coupling efficiency. The conversion rate of HMF and yield of FDCA reach 98.7% and 98.8%, respectively, even when the concentration of HMF is as high as 300 mM.
研究领域:
电化学
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催化
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材料科学
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可再生能源
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DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
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IF 7.2
Mengyuan Qiu,Yongzhi Xiong,Wei Zhao,Dong Ouyang,Zongxuan Wu,Tangtianxiang Liang,Changzhou Chen,Shengchun Hu,Hao Sun
Designing low-cost, high-performance electrocatalysts for the electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to produce 2,5-furandicarboxylic acid (FDCA) remains a significant challenge. Herein, we report a novel post-pyrolysis phosphidation method for preparing Nb- and Fe-doped CoP-based catalysts. Nb-CoP@NC delivers a current density of 91.79 mA cm⁻² at a potential of only 1.50 V vs. RHE, achieving nearly 100 % HMF conversion, 98.3 % FDCA selectivity, and 95.6 % Faradaic efficiency (FE). Structural and surface analyses via XRD and XPS reveal that Nb doping significantly modulates the electronic structure of CoP, generating Nb 5+δ active species, which show superior catalytic activity for HMFOR compared to Fe 3+δ . This work not only highlights the pivotal role of Nb doping in enhancing catalytic performance but also provides a general and facile strategy for constructing efficient bimetallic CoP-based catalysts for biomass-derived HMF oxidation.
研究领域:
催化
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电化学
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生物质转化
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材料科学
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
Materials
·
2025
·Vol. 18
·期 16
·3780
·
IF 3.2
Lei Yang,Anbang Duan,Zhanyin Liu,Tingying Wei,Chunzhao Liu
Aiming to address the key challenges of poor enzyme stability, difficult recovery, and difficult synergistic optimization of catalytic efficiency in high-value conversion of biomass, this study utilizes mineralization self-assembly technology to combine laccase with Fe3O4@SiO2-PMIDA-Cu2+composite, constructing magnetic laccase nanoflower (MLac-NFs) materials with a porous structure and superparamagnetism. This synthetic material can efficiently catalyze the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). The characterization results indicated that MLac-NFs exhibit optimal catalytic activity (63.4 U mg−1) under conditions of pH 6.0 and 40 °C, with significantly enhanced storage stability (retaining 94.26% of activity after 30 days of storage at 4 °C). Apparent kinetic analysis reveals that the substrate affinity and maximum reaction rate of MLac-NFs were increased by 38.3% and 439.6%, respectively. In the laccase–mediator system (LMS), MLac-NFs mediated by 30 mM TEMPO could achieve complete conversion of HMF to FDCA within 24 h. Moreover, due to the introduction of magnetic nanoparticles, the MLac-NFs could be recovered and reused via an external magnetic field, maintaining 53.26% of the initial FDCA yield after six cycles.
研究领域:
生物催化
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生物质转化
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绿色化学
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纳米材料
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酶工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Biomass Conversion and Biorefinery
·
2023
·
IF 4
Liu Yun,Wang Xueke,Hu Mingyang,Yu Yanyan
2,5-furandicarboxylic acid (FDCA), one of the most important building blocks, has attracted tremendous concerns, and the routes for FDCA synthesis from non-edible hemicellulose are of vital importance from the views of the circular economy. Herein, a multistep process towards hemicellulose-to-FDCA conversion is proposed, including hemicellulose-to-furfural conversion and sequential oxidation to furoic acid (FA), following with cesium furoate (FA-Cs) preparation and its direct carboxylation with carbon dioxide (CO 2 ). The overall conversion yield of the targeted FDCA product towards the hemicellulose-to-FDCA pathway reaches 29.6%. Many efforts are made on the direct carboxylation reaction of FA-Cs with CO 2 using Cs 2 CO 3 as a catalyst. Results show that FDCA with 56.47% yield is achieved via direct carboxylation of FA-Cs at 290 °C for 12 h with 40 mL/min of flowing CO 2 . Different from the previous reports, it is demonstrated that drying methods of FA-Cs show significant effects on the yield and properties of the targeted FDCA product. It is found that the conventional drying method is more suitable than the vacuum drying method. From the putative reaction mechanism, the roles of CO 2 and Cs 2 CO 3 are elucidated. CO 2 plays a direct role in carboxylation reaction, and excessive Cs 2 CO 3 can deteriorate FDCA yield due to the occurrence of decomposition. Interestingly, biochar generated during carboxylation reaction is a promising potential adsorbent, which can efficiently adsorb methylene blue with a removal rate of 96% and an adsorption amount of 80 mg/g. This present work can provide an integrated strategy for both hemicellulose valorization and CO 2 utilization in future.
研究领域:
化学工程
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绿色化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2016
·
IF 5.267
Yanbing Wang,Kai Yu,Da Lei,Wei Si,Yajun Feng,Lan-Lan Lou,Shuangxi Liu
An environmentally benign and homogeneous base-free route for 5-hydroxymethyl-2-furfural (HMF) aerobic oxidation to 2,5-furandicarboxylic acid (FDCA) in water was reported using Mg–Al–CO3 hydrotalcite-supported Pd nanoparticles (xPd/HT-n) as catalyst. The influences of the Mg/Al molar ratio of hydrotalcite and Pd loading amount on the catalytic performance of these catalysts were originally systematically investigated. These catalysts exhibited excellent catalytic activity and FDCA selectivity in the HMF oxidation, especially for 2%Pd/HT-5 and 2%Pd/HT-6; >99.9% FDCA yields were achieved for 8 h under ambient pressure and homogeneous base-free conditions. The remarkably improved catalytic performance could be attributed to the suitable basicity of the Mg–Al–CO3 hydrotalcite and the abundant OH– groups on the surface of hydrotalcite. The plausible reaction mechanism was proposed based on the results of a series of controlled experiments. Furthermore, these catalysts were quite stable and could be reused at least five times without obvious loss in reaction activity.
研究领域:
催化
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化学工程
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材料科学
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环境化学
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Nano
·
2023
·
IF 10.3
R. Zhang,F. Gao,C. Yang,Y. Bian,G. Wang,K. Xue,J. Zhang,C. Wang,X. Gao
Coupling electrocatalytic 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) with hydrogen evolution reaction (HER) is capable of potentially enhancing energy efficiency for hydrogen production and converting biomass into high-valued products. Herein, a novel metallic heterostructure based on Ni 3 S 2 and Co 9 S 8 (Co 9 S 8 @Ni 3 S 2 /NF) was designed for H 2 production and selective oxidation of HMF into 2, 5-furandicarboxylic acid (FDCA). Benefiting from the merit of metal heterojunction, Co 9 S 8 @Ni 3 S 2 /NF not only possesses appropriate H∗ adsorption energy , but also promotes the adsorption and desorption process of organic, thus making reaction dynamics for both HER and HMFOR more exceptional. Furthermore, the anion exchange membrane (AEM) electrolyzer with Co 9 S 8 @Ni 3 S 2 /NF as anode and cathode electrodes toward HMFOR and HER only required a low potential of 1.61 V for continuous hydrogen and FDCA production at the initial current density of 50 mA/cm 2 . The generation rate of H 2 and FDCA are as high as 45.6 L/h/m 2 and 7.25 mg/h/cm 2 , corresponding to the Faraday efficiency of ∼100% and 93.0%, respectively. The in-situ Raman and theoretical calculations demonstrated that the electron transfer from Ni 3 S 2 to Co 9 S 8 at heterogeneous interface contributes to the formation of Ni/Co–OOH, which is the active species of HMFOR.
研究领域:
电化学
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材料科学
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能源工程
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催化
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化工
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2024
·
IF 4.3
Hongliang Dai,Pengjie Zhou,Shenming Yang,Lili Yang,Hongye Bai,Cui Dai,Guohai Xu,Weiqiang Fan
Electrocatalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is significant for the sustainable production of value-added chemicals. Active sites of catalysts could enhance the activity and selectivity of the HMF oxidation reaction (HMFOR), but the self-healing ability of active sites has been commonly ignored. In this work, Co(OH)2/Ni-MOF was successfully fabricated for efficient oxidation of HMF to FDCA under mild conditions. Electrochemical and cyclic stability experiments demonstrated the high self-healing properties of the dual active sites (Co3+/Ni3+). So, the retention rate of FDCA yield can still reach 98.5%, even after 90 days. HMFOR was further coupled with 4-nitrophenol hydrogenation, which promotes the yield and Faradaic efficiency of FDCA to about 100%. Therefore, this study explores the self-healing properties of species and provides new insights for designing efficient catalysts.
研究领域:
电化学
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催化
·
可持续化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Biotechnology for Biofuels and Bioproducts
·
2023
·Vol. 16
·期 1
·1-13
·
IF 0
Yang Fan,Liu Jiashu,Li Bianxia,Li Huanan,Jiang Zhengbing
Background As a cost-effective and eco-friendly approach, biocatalysis has great potential for the transformation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA). However, the compatibility of each enzyme in the cascade reaction limits the transformation efficiency of HMF to FDCA. Results Coupled with an alcohol oxidase from Colletotrichum gloeosporioides ( Cgl AlcOx), this study aims to study the potential of bacterial laccase from Bacillus pumilus ( Bp Lac) in an enzymatic cascade for 2,5-furandicarboxylic acid (FDCA) biosynthesis from 5-hydroxymethylfurfural (HMF). Bp Lac showed 100% selectivity for HMF oxidation and generated 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). Cgl AlcOx was capable of oxidizing HMFCA to 2-formyl-5-furancarboxylic acid (FFCA). Both Bp Lac and Cgl AlcOx could oxidize FFCA to FDCA. At the 5 mM scale, a complete transformation of HMF with a 97.5% yield of FDCA was achieved by coupling Bp Lac with Cgl AlcOx in the cascade reaction. The FDCA productivity in the reaction was 5.3 mg/L/h. Notably, Bp Lac could alleviate the inhibitory effect of FFCA on Cgl AlcOx activity and boost the transformation efficiency of HMF to FDCA. Moreover, the reaction was scaled up to 40 times the volume, and FDCA titer reached 2.6 mM with a yield of 58.77% at 168 h. Conclusions This work provides a candidate and novel insight for better design of an enzymatic cascade in FDCA production.
研究领域:
生物催化
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生物化学
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化学工程
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酶学
✓ 已验证
产品关联
DOI
PubMed
Nature Communications
·
2023
·Vol. 14
·期 1
·1-12
·
IF 16.6
Zhou Hua,Ren Yue,Yao Bingxin,Li Zhenhua,Xu Ming,Ma Lina,Kong Xianggui,Zheng Lirong,Shao Mingfei,Duan Haohong
Electrooxidation of biomass platforms provides a sustainable route to produce valuable oxygenates, but the practical implementation is hampered by the severe carbon loss stemming from inherent instability of substrates and/or intermediates in alkaline electrolyte, especially under high concentration. Herein, based on the understanding of non-Faradaic degradation, we develop a single-pass continuous flow reactor (SPCFR) system with high ratio of electrode-area/electrolyte-volume, short duration time of substrates in the reactor, and separate feeding of substrate and alkaline solution, thus largely suppressing non-Faradaic degradation. By constructing a nine-stacked-modules SPCFR system, we achieve electrooxidation of glucose-to-formate and 5-hydroxymethylfurfural (HMF)-to-2,5-furandicarboxylic acid (FDCA) with high single-pass conversion efficiency (SPCE; 81.8% and 95.8%, respectively) and high selectivity (formate: 76.5%, FDCA: 96.9%) at high concentrations (formate: 562.8 mM, FDCA: 556.9 mM). Furthermore, we demonstrate continuous and kilogram-scale electrosynthesis of potassium diformate (0.7 kg) from wood and soybean oil, and FDCA (1.17 kg) from HMF. This work highlights the importance of understanding and suppressing non-Faradaic degradation, providing opportunities for scalable biomass upgrading using electrochemical technology.
研究领域:
化学工程
·
电化学
·
可持续化学
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生物质转化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Xuemin Zhong,Peng Yuan,Yanfu Wei,Dong Liu,Dusan Losic,Mengyuan Li
The aerobic oxidation of 5-hydroxymethylfurfural (HMF), a key platform compound derived from biomass, to 2,5-furandicarboxylic acid (FDCA) is a highly important reaction in the production of green and sustainable chemicals. Here, we developed a highly efficient and stable halloysite-supported Pt–Au alloy catalyst for the selective oxidation of HMF to FDCA. The catalyst was synthesized through the organosilane functionalization of halloysite nanotubes, followed by the in situ formation and dispersion of Pt–Au alloy nanoparticles on the internal and external surfaces of nanotubes. The composition, morphology, and structure of the prepared catalyst were characterized. The catalyst with the optimal composition of Pt/Au molar ratio of 1/4 and metal loading of 1.5 wt % exhibited outstanding catalytic activity for the oxidation of HMF to FDCA using O2 as an oxidant with 100% conversion of HMF and 99% selectivity of FDCA. This excellent catalytic performance is mainly attributed to the high dispersion and alloying effects of bimetallic nanoparticles, which promoted the activation of reactants or intermediates and further improved FDCA selectivity. Furthermore, the halloysite-supported Pt/Au bimetallic catalyst showed high stability and reusability. This study provides a promising strategy by combining clay mineral halloysite and bimetallic alloys for developing efficient catalysts with high FDCA selectivity and stability for the oxidation of HMF to FDCA.
研究领域:
催化
·
纳米材料
·
绿色化学
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可持续化学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）