Biomass Conversion and Biorefinery
·
2022
·
IF 4.05
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.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2025
·
IF 9
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.
研究领域:
化学工程
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可持续发展
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电催化
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DOI
高影响因子
ChemSusChem
·
2021
·Vol. 15
·期 13
·e202101983
·
IF 8.928
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.
研究领域:
催化化学
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材料科学
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生物质转化
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产品关联
DOI
PubMed
高影响因子
CATALYSIS TODAY
·
2024
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IF 5.2
Yang Gao,Shilin Fan,Bin Zhu,Soliman I. El-Hout,Jinghui Lyu,Jian Zhang,Chunlin Chen
Biomass energy has gained significant attention due to its renewability and clean, low-carbon characteristics. We prepared a Co@NC-a catalyst using the complexation-carbonation-acid etching method, which can catalyze both thermochemical and electrochemical HMF selective oxidation reactions. In thermocatalysis, it can achieve 100 % HMF conversion and 94.4 % FDCA yield at 65 °C and 0.2 MPa O 2 . In electrocatalysis , 100 % HMF conversion and 73 % FDCA yield were also realized. Significantly, graphitized carbon contributes to the aerobic oxidation of HMF due to its excellent electrical conductivity , which promotes electron transfer during the reaction. Additionally, a comparative study of the activation energy of this catalytic system in electrocatalysis and thermocatalysis showed that electrocatalysis is kinetically more favorable. The energy efficiency calculation also indicates electrocatalysis is more energy efficient than thermocatalysis.
研究领域:
生物质能
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催化化学
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材料科学
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产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
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2024
·
IF 6.3
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
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材料科学
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产品关联
DOI
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
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可再生资源化学
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DOI
高影响因子
INORGANIC CHEMISTRY COMMUNICATIONS
·
2025
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IF 5.4
Wei Zhao,Mengyuan Qiu,Yajun Liu,Yingrui Dong,Xiaojing Huang,Siyue Li,Feifei Lin,Yongzhi Xiong,Changzhou Chen
The lack of high-performance, low-cost electrocatalysts is the key challenge for the production of 2,5 furandicarboxylic acid via electrocatalytic oxidation of 5-hydroxymethylfurfural. In this work, we report a novel approach for the preparation of highly dispersible transition metal catalysts loaded by carbon aerogel-loaded via a chitosan-transition-metal-ion coordination. The experimental results demonstrated that all of Ni 2+ , Co 2+ and Cu 2+ were able to coordinate with chitosan to form stable gels, which were then pyrolyzed to obtain highly dispersed transition metal-based catalysts (Co@NC, Ni@NC and Cu@NC) The Cu@NC exhibited the best HMFOR activity with high HMF conversion (nearly 100 %), FDCA selectivity (98.1 %), and Faraday efficiency (95.3 %). Mechanistic studies showed that Cu@NC was able to accumulate more effective oxidatively active species and thus achieve higher HMFOR current density compared to Co@NC and Ni@NC, and that the electrooxidation of HMF at the Cu@NC electrode followed the HMFCA oxidation pathway. This study provides a general and facile strategy for macropreparation of highly dispersible carbon aerogel-loaded transition metal catalysts for efficient electrocatalytic valorization of HMF.
研究领域:
材料科学
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电化学
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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
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材料科学
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可再生资源
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产品关联
DOI
高影响因子
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2024
·
IF 2.2
Peng Wang,Jun-Fei Gu,Zhan Chen,Hao-Yue Ma,Xing-Chuan Li,Shuai Li,Xiang-Ya Xu,Ye Yuan,Cheng Chen,Zongkui Kou
Graphical This study develops a solid-state thermal (SST) synthesis method for the one-step preparation of MOF-derived Mn x @NC catalysts. Among these, the optimal catalyst (Mn 2.5 @NC) exhibits excellent activity, remarkable stability, and good recyclability for HMF oxidation to FDCA, achieving an FDCA yield of 94 % within 4 h at room temperature and maintaining its catalytic performance for five cycles without activity decay. Transforming the bio-based 5-hydroxymethylfurfural (HMF) into its oxidation product 2,5-furandicarboxylic acid (FDCA) offers an attractive route for synthesizing bioplastic monomers. However, significant challenges remain in developing efficient and stable non-precious metal catalysts. Here, we employed a solid-state thermal synthesis (SST) method to design and synthesize a series of metal-organic framework (MOF)-derived metal-nitrogen-carbon (M@NC) materials with gradient metal contents and low metal loadings, labeled as Mn x @NC, for converting HMF into FDCA through oxidation. Further investigations revealed that the amount of metal doping significantly influenced the catalyst structure, particularly in terms of defect quantity and specific surface area. The optimal catalyst, Mn 2.5 @NC, exhibited the largest specific surface area and the highest number of defects, achieving a 94 % FDCA yield within 4 h. Experimental results demonstrated that the recovered catalyst could be reintroduced into the reaction system and maintained selectivity comparable to that of the fresh catalyst for at least five cycles. Moreover, various characterizations of both fresh and recovered catalysts confirmed the great stability of Mn 2.5 @NC. This study provides advanced insights into the effective catalytic conversion of HMF to FDCA and highlights the importance of structural design and regulation in optimizing M@NC catalysts.
研究领域:
化学工程
·
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2019
·
IF 4.888
Tianyu Gao,Yongxuan Yin,Guanghui Zhu,Qiue Cao,Wenhao Fang
Oxidative transformations of HMF are key routes toward a wide variety of chemicals and biofuels through an environmental friendly process. Co 3 O 4 NPs decorated Mn-Co-O solid solution, donated as Co 3 O 4 /Mn X Co, was prepared by co-precipitation method and used as non-precious metal catalyst for base-free oxidation of HMF to FDCA in the presence of O 2 and water. Comprehensive characterizations such as XRD, H 2 -TPR, O 2 -TPD, XPS, NH 3 /CO 2 -TPD and TEM were used to study materials properties especially the oxygen mobility and acidity-basicity. The effect of Mn/Co molar ratio in catalyst and the reaction conditions were investigated and optimized. In addition, the kinetics of the reaction was monitored to reveal the reaction route and rate-determining step. The variation of Mn/Co molar ratio was found to affect not only HMF conversion but also distribution of products. When the Mn/Co ratio was of 0.2, the Co 3 O 4 /Mn 0.2 Co catalyst showed the optimal catalytic performance (i.e., >99% yield of FDCA obtained under 1 bar O 2 at 140 °C after 24 h) due to the highest content of both Lewis and Brønsted acid sites on the surface, leading to the strongest ability of HMF adsorption and COOH group formation, as well as the enhanced oxygen mobility. This catalyst was shown stable after a minor deactivation (≤8%) during six recycling uses and its activity can be entirely regenerated by calcination in air.
研究领域:
催化化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED POWDER TECHNOLOGY
·
2020
·
IF 4.217
Yekun Zhu,Yun Zhang,Lili Cheng,Mohammed Ismael,Zhiyuan Feng,Ying Wu
The g-C 3 N 4 /NaNbO 3 photocatalyst was synthesized by simply calcining the mixture of NaNbO 3 and melamine. The synthesized composite exhibits high photocatalytic performance in the selective oxidation of 5-Hydroxymethylfurfural (HMF) to 5-formyl-2-furancarboxylic acid (FFCA) when using water as solvent. The structure and composition of g-C 3 N 4 /NaNbO 3 photocatalysts were characterized by TG, XRD, SEM, UV–Vis, FT-IR, and XPS methods, and the optical and electrochemical properties were investigated by EIS, PC, and PL techniques. O 2 − was inferred to be the primary active species in this process based on the active species trapping experiment. Heterostructure formation of g-C 3 N 4 /NaNbO 3 composites efficiently promoted the separation of photo-generated electron-hole pairs and accelerated the electron transfer rate, thus reduced the formation of OH, and sequentially improved the selectivity of FFCA. The highest HMF conversion of 35.8% with FFCA selectivity of 87.4% was achieved on C/N-59.6 photocatalyst under the irradiation of visible light. The possible mechanism and reaction route were also proposed.
研究领域:
化学
·
环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Physics
·
2023
·
IF 11.5
Zhenfei Yang,Xinnian Xia,Ming Fang,Longlu wang,Shuaijun Pan,Yang guo
Efficient spatial separation of photogenerated carriers is the key to achieving photocatalytic oxidation reduction synergistic reactions, and the built-in electric field generated by piezoelectric effects can provide a strong driving force for charge separation. A novel Pt/ZnIn 2 S 4 /BaTiO 3 (PBZIS) piezo-photocatalyst with spatial charge separation was successfully constructed through two-step hydrothermal and photodeposition methods. Due to the special 1D/2D core/shell structure, the inner BaTiO 3 can served as hole-storage layer, while the outer Pt nanoparticles can acted as electron capture center, thus greatly improving the separation of photo generated charge carriers and achieving spatial separation of redox sites. Under the ultrasound, the polarized electric field induced by the piezoelectric effect can further improve the extraction rate of photo generated holes by BaTiO 3 and accelerate surface catalytic reactions . Therefore, the synergism of electron/hole co-extraction and piezoelectric effect construct a directional transmission channel and target active sites for photogenerated electron-holes over PBZIS heterojunctions , reuslting in the highest performance for photocatalytic cooperative H 2 evolution (1335.3 μmol g −1 h −1 ) and HMF oxidation (1070.8 μmol g −1 h −1 ). This work would inspire the development of high-performance piezo-photocatalysts for the cooperative biomass oxidation coupling with high efficient hydrogen evolution .
研究领域:
材料科学
·
能源科学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）