Small
·
2024
·
IF 13
Ming Li,Haixin Sun,Chen Wang,Yongzhuang Liu,Qinqin Xia,Juan Meng,Haipeng Yu,Shuo Dou
The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) represents an environmentally friendly approach to generate high-value-added chemicals from biomass. The successful electrochemical transformation of HMF during the oxidation reaction (HMFOR) necessitates an ideal adsorption interaction between HMF and OH − on the electrode surface. Yet, catalysts with a singular active site offer limited flexibility in managing the competitive adsorption of HMF and OH − . To this end, different active sites are customized in this work to construct a P and N co-doped porous carbon that wrapped Co 3 O 4 (Co 3 O 4 @PNC). Co-doping with these two heteroatoms generates C 3 P = O and pyrrolic N as adsorption sites to better balance the adsorption of HMF and OH − , respectively, rather than promoting competition between the HMF and OH − on a single active site. With this design strategy, Co 3 O 4 @PNC demonstrates significant HMFOR activity, the conversion rate of HMF surpassed 99% with a 2,5-furandicarboxylic acid (FDCA) yield exceeding 95% after 2 h of electrolysis. Furthermore, it shows universal applicability in the electrooxidation of other alcohol/aldehyde substrates, yielding efficiencies of 90–99%. This work not only provides guidance for advanced electrocatalysts design toward alcohol/aldehyde oxidation but also offers insights into the utilization of biomass-derived platform chemicals.
研究领域:
催化材料科学
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电化学工程
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生物质转化
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DOI
PubMed
高影响因子
Catalysts
·
2025
·Vol. 15
·期 12
·1160
·
IF 4
Liya Zheng,Yongshui Qu,Yibing Li,Yuanxin Cao,Quanyuan Wei,Ming Fang
To address the challenges of difficult recovery, significant environmental hazards associated with homogeneous catalysts, and insufficient catalytic activity of heterogeneous supports in the catalytic dehydration of fructose to produce 5-hydroxymethylfurfural (5-HMF), this study employs a straightforward nitric acid modification method to prepare an acid-activated silica gel catalyst for application in this reaction system. Through systematic investigation of the influence of modification conditions on catalyst performance and economic benefits, optimal reaction conditions were determined: DMSO as the solvent, nitric acid-modified silica gel as the catalyst, a reaction temperature of 120 °C, a solid–liquid ratio of 1:30 (g∙mL−1), and a fructose-to-catalyst mass ratio of 1:1. Under these conditions, the maximum 5-HMF yield reached 91.6%. Characterization via specific surface area, pore size analysis, and acid/base site characterization (NH3-TPD) revealed that nitric acid modification preserved the silica gel’s pore structure. Through oxidative cleaning, etching to expose silanol groups, and inducing surface defects, this process significantly increased the number of acid sites on the silica gel surface, thereby enhancing catalytic activity. This study presents a low-cost, easily recoverable, and environmentally friendly heterogeneous catalytic strategy for the efficient conversion of fructose into 5-HMF. It also provides experimental guidance for the targeted functionalization of silica-based catalytic materials, holding significant implications for advancing the high-value utilization of biomass resources.
研究领域:
催化化学
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绿色化学
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生物质能源
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材料科学
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化学工程
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2026
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IF 9.1
Shan Yue,Jiayi Gao,Hui Kan,Ting Zhang,Xiangdong Ma,Rui Liu,Mingjing Zhao,Xiaohong Xia
Modulating the electrocatalytic interface is key to efficiently converting 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA). Herein, a NiCo( OH ) x /NiCoMoO 4 heterojunction electrocatalyst is constructed. The high-valence Mo 6+ substrate acts as an electron regulator, creating electron-deficient Ni sites and promoting the formation of active Ni 3+ species for HMF oxidation. Operando analysis and distribution of relaxation times (DRT) studies confirm that the Mo 6+ substrate enhances charge transfer and mass transport. This special electronic structure directs selective aldehyde group activation, steering the reaction along the HMFCA pathway. The obtained catalyst achieves a 91.4% FDCA yield with 96% Faradaic efficiency at 1.4 V vs. RHE. This work demonstrates a dual modulation strategy via high oxidation state substrate for efficient biomass conversion.
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高影响因子
ChemSusChem
·
2024
·
IF 7.5
Xingyu Luo,Cheng Xie,Zhefei Zhao,Meiqin Shi,Huajun Zheng
Graphical Volcano plots are highly effective for understanding catalyst mechanisms and rational designing high-performance catalysts, particularly across different metals. However, the understanding of the relationship between different metals and their reaction mechanisms in 5-Hydroxymethylfurfural (HMF) reduction reactions is still limited. In this study, we explore the Gibbs free diagram of HMF reduction reactions on different metal surfaces and construct a volcano plot that connects HMF adsorption energy with the energy barriers of the rate-determining step. This provides a deeper understanding of HMFRR. Our theoretical findings align well with experimental results. Furthermore, we selectively constructed an AgPb bimetal interface based on our volcano plot, which boosted the catalyst activity. DFT calculations revealed that the AgPb bimetal surface effectively adjusts HMF adsorption energy and reduces energy barriers, suggesting that rational designing bimetal catalysts based on volcano plots is efficient. 2,5-bis(hydroxymethyl)furan (BHMF) derived from 5-Hydroxymethylfurfural (HMF) through a hydrogenation process has extensive applications in the production of resins, polymers, and artificial fibers. However, screening out the candidate and then modulating the active site to optimize the catalyst for high yield of BHMF are currently insufficient. In this study, Gibbs free energy diagrams of the reduction of HMF on 13 metals were presented, along with the identification of the rate-determining step (RDS) with the highest reaction barrier for each metal. We attempted to construct a volcano plot for HMFRR reaction. Additionally, a strategy was proposed to adjust the reaction barriers of RDS by combining two appropriate metals. Further experiments confirmed that Pb with the lowest energy barrier exhibited the highest HMF conversion (BHMF selectivity) among single metals. The modified catalyst by doping Ag on Pb, further boosted the HMF conversion (BHMF selectivity) from 42.1 % (59.4 %) to 80.8 % (80.9 %), respectively. These results provide an approach to rationally design and construct the catalyst system for efficient conversion of HMF.
研究领域:
催化化学
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材料科学
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理论计算
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DOI
PubMed
高影响因子
Green Energy & Environment
·
2021
·
IF 8.207
Sen Luan,Wei Li,Zanwu Guo,Wenxiu Li,Xiaojian Hou,Yi Song,Ran Wang,Qian Wang
Well-ordered hierarchically mesoporous/microporous carbon materials have been successfully fabricated by using dual soft-templating approach through compressed CO 2 . Pluronic F127 and different type of surfactants, including nonionic, cationic, and anionic surfactants, were used as dual templates to investigate the influence on the morphology and nanostructure of the as-prepared carbon samples. TEM, SEM, N 2 sorption, wide-angle and small-angle XRD analysis were employed to reveal the well-ordered hierarchically micro-mesoporous structure with 2D hexagonal symmetry by using compressed CO 2 . The prepared HPC samples with different pressures as the catalyst carriers have been functioned by chlorosulfonic acid for the fructose conversion into HMF. Chlorosulfonic acid concentration, catalyst dosage and reaction temperature have been optimized for fructose-to-HMF transformation with the obtained catalyst. The performances of as-made HPC–SO 3 H samples in HMF yield and reaction rate of fructose-to-HMF transformation have been investigated. The stability of the samples was also conducted in the dehydration of fructose to HMF for five cycles. The possible catalytic mechanism by using hierarchically porous carbon materials as catalyst support for fructose-to-HMF transformation was proposed.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
AICHE JOURNAL
·
2017
·Vol. 63
·期 11
·4920-4932
·
IF 2.836
Yunlei Zhang,Pei Jin,Meng Liu,Jianming Pan,Yongsheng Yan,Yao Chen,Qingang Xiong
In this work, a novel route to deconstruct cellulose into 5-hydroxymethylfurfural (HMF) by cascading enzymatic and chemical reactions is reported. For biocatalyst preparation, Fe 3 O 4 nanoparticles encapsulated SBA-15 with appropriate pore size was synthesized and utilized as magnetic scaffolds for the immobilization of cellulase. For chemical catalyst preparation, sulfated zirconium dioxide conformed monolayers were grafted on SBA-15 template to create thermally robust mesoporous catalysts with tunable solid basic/Lewis acid and Brønsted acid sites. Catalytic performance of biocatalyst and chemical catalyst was explored in the aqueous phase conversion of IL pretreated cellulose to glucose, and in the iPrOH/water solvent conversion of glucose to HMF conversion, respectively. After the optimization of reaction conditions, a sequential conversion of pretreated cellulose to glucose and glucose to HMF was performed, and 43.6% HMF yield can be obtained. The cascaded enzymatic and chemocatalytic reaction system demonstrates an effective and economically friendly process for biomass energy conservation. A novel route for green conversion of IL pretreated cellulose to 5-hydroxymethylfurfural (HMF) by cascading an enzymatic catalysis in an aqueous system with chemocatalysis in an iPrOH/water solvent mixture is reported. © 2017 American Institute of Chemical Engineers AIChE J , 2017
研究领域:
生物化学
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可再生能源
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DOI
高影响因子
International Journal of Chemical Engineering
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2014
·
IF 0
Hu Li,Song Yang
L-Proline derived ionic liquids (ILs) used as both solvent and catalyst were efficient for transformation of fructose and sucrose to 5-hydroxymethylfurfural (HMF) in the presence of water. Response surface methodology (RSM) was employed to optimize fructose dehydration process, and a maximum HMF yield of 73.6% could be obtained at 90°C after 50 min. The recycling of the IL exhibited an almost constant activity during five successive trials, and a possible reaction mechanism for the dehydration of fructose to HMF was proposed.
研究领域:
化学工程
·
催化反应
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DOI
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Xiaoqi Lyu,Hong Li,Huaizhong Xiang,Yibing Mu,Na Ji,Xuebin Lu,Xiaolei Fan,Xin Gao
Microwave (MW)-assisted process intensification of catalytic conversion of saccharides is a promising route for energy efficient production of value-added chemicals and fuels. This work presents the development of the MW-responsive catalysts (i.e., the acid functionalized spherical carbon superstructure, SCS) for converting fructose to 5-HMF effectively and efficiently under MW irradiation. Under a mild MW condition (at 70 °C, atmospheric pressure), the SCS catalyst (with surface sulfonic and carboxylic acid groups) achieved fructose conversion of ~ 97.8% and selectivity to 5-HMF of ~ 90.6% after 5 min reaction time with good recyclability, being significantly higher than that obtained by the system under the conventional heating. Importantly, the MW-assisted system showed very high energy efficiency coefficient of 1.01 mmol kJ −1 L −1 compared to that (0.09 mmol kJ −1 L −1 ) of the conventional thermal catalysis. The mechanism of process intensification of the system developed may be attributed to the combination of the dipole polarization of the MW-responsive sulfonic groups and the selective heating of the MW-absorbing SCS support under the MW condition.
研究领域:
化学工程
·
催化科学
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DOI
高影响因子
DALTON TRANSACTIONS
·
2023
·Vol. 52
·期 7
·1950-1961
·
IF 4
Jingjing Fan,Yin Zhao,Qian Wang,Mingyu Gao,Xintao Li,Dianqing Li,Junting Feng
Aiming at the comprehensive utilization of waste carbon resources and renewable carbon resources, we put forward the photocatalytic coupling process of CO2 reduction and 5-hydroxymethylfurfural (5-HMF) oxidation mediated by the anionic compound of layered double hydroxides (LDHs). Specifically, a ZnNiFe–LDH was synthesized by co-precipitation method, during which CO2 was stored between LDH layers in the form of carbonate. Then, a certain amount of metal vacancies were introduced into LDH nanosheets by selectively etching Zn2+ ions. ICP-AES, EPR and XPS showed that the concentration of Zn vacancies gradually increased with the etching time prolonging, which thus optimized the electronic structure of LDH layers. Under the catalysis of the electron-rich metal cations and hydroxyl groups on the layers, the interlayer carbonate was in situ reduced into CO coupled accompanied with the 5-HMF oxidation to 2.5-furandiformaldehyde (DFF). Compared with the unetched ZnNiFe–LDHs, the CO and DFF yields over the LDHs etched for 3 h were increased by 2.84 and 2.82 times under UV-vis irradiation with a density of 500 mW cm−2. Finally, combined with isotope-labeled 13CO2 experiments and in situ FTIR characterization, we revealed the possible coupling mechanism and defect-induced performance enhancement mechanism.
研究领域:
环境科学
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材料科学
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化学工程
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DOI
PubMed
高影响因子
Journal of Energy Chemistry
·
2024
·
IF 14
Peiyun Zhou,Haokun Pan,Guangtong Hai,Xiang Liu,Xiubing Huang,Ge Wang
In this work, nickel foam supported CeO 2 -modified CoBDC (BDC stands for terephthalic acid linker) metal-organic frameworks (NF/CoBDC@CeO 2 ) are prepared by hydrothermal and subsequent impregnation methods, which can be further transformed to NF/CoOOH@CeO 2 by reconstruction during the electrocatalytic test. The obtained NF/CoOOH@CeO 2 exhibits excellent performance in electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) because the introduction of CeO 2 can optimize the electronic structure of the heterointerface and accelerate the accumulation of *OH. It requires only a potential of 1.290 V RHE to provide a current density of 50 mA cm −2 in 1.0 M KOH + 50 mM HMF, which is 222 mV lower than that required in 1.0 M KOH (1.512 V RHE ). In addition, density-functional theory calculation results demonstrate that CeO 2 biases the electrons to the CoOOH side at the heterointerface and promotes the adsorption of *OH and *HMF on the catalyst surface, which lower the reaction energy barrier and facilitate the electrocatalytic oxidation process.
研究领域:
材料科学
·
电化学
·
理论计算
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DOI
高影响因子
INORGANIC CHEMISTRY COMMUNICATIONS
·
2025
·
IF 5.4
Tursunjan Aydan,Nuermaimaiti Yimamu,Ding Kaize,Yao Zhengzheng,Guan Qingqing
Metal-organic frameworks (MOFs), particularly UiO-66, offer advantages in biomass catalytic conversion due to their good thermal stability, tunable porosity and abundant active sites. However, agglomeration limits their catalytic efficiency. To address this, a series of acid-base bifunctional UiO-66-type catalysts supported on biochar (BC) was developed in green solution through a one-pot method. BC prepared by pyrolyzing cotton stalks (CS) under N 2 atmosphere at high temperature and activated before use. The physico-chemical properties of materials were studied by various characterization methods, and their catalytic performance for converting cellulose to 5-hydroxymethylfurfural (5-HMF) in [BMIM]Cl ionic liquid was evaluated. Reaction parameters such as catalyst type, catalyst loading, temperature and time were optimized. Under the optimized conditions, achieving a 5-HMF yield of 46.58 %. The BC-supported catalyst NH 2 -UiO-66-SO 3 H/BC exhibited significantly higher catalytic activity than its unsupported counterpart and increased the 5-HMF yield by 23.78 %. This performance improvement is attributed to the grafted sulfonic/amino groups, which enhance the catalytic performance by improving the dispersion of UiO-66 upon the introduction of BC. This work demonstrates biochar-supported UiO-66 as an effective strategy for enhancing catalytic efficiency in sustainable biomass valorization to platform chemicals.
研究领域:
催化
·
生物质高值化
·
绿色化学
·
材料科学
·
可持续能源
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 13.2
Ting Xiang,Kang Chen,Siqi Ni,Xijun Wang,Changlun Chen
The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) offers an eco-friendly route to produce 2,5-furandicarboxylic acid (FDCA). Coupling this anodic reaction with the hydrogen evolution reaction provides a sustainable alternative to oxygen evolution reaction in water electrolysis, enhancing energy efficiency while generating green hydrogen. However, conventional nickel-based catalysts suffer from weak substrate adsorption and limited active-site utilization. Here, we introduce a ligand-engineered charge-transfer complex, Ni(TCNQ) 2 (H 2 O) 2 , in which π-conjugated TCNQ ligands enable strong π–π stacking with the furan ring of HMF to enrich substrate adsorption, while the electron-accepting nature of TCNQ mediates metal-ligand charge transfer to regulate the Ni 2+ /Ni 3+ redox couple. This dual function significantly accelerates reaction kinetics and stabilizes intermediates, enabling Ni(TCNQ) 2 (H 2 O) 2 to deliver 100 mA·cm −2 at 1.38 V and nearly 100 % FDCA yield. Mechanistic insights from X-ray photoelectron spectroscopy, operando Raman, and density functional theory (DFT) confirm that ligand-driven adsorption and electron interactions accelerate the catalytic process. DFT free-energy profiles further demonstrate that Ni(TCNQ) 2 (H 2 O) 2 smooths the reaction energy landscape, lowering the thermodynamic barriers compared with Ni(OH)₂. This work underscores the pivotal role of ligand engineering in tuning catalytic interfaces for efficient biomass electrooxidation and green hydrogen co-production in integrated renewable energy systems.
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高影响因子
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