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JOURNAL OF CATALYSIS · 2025 · IF 6.5

Ionic liquids modified electrochemical interfaces for enhanced biomass valorization

Xinyu Liu,Jiansong Wang,He Li,Xiaoliang Qu,Yipu Xu,Liu-Liu Shen,Gui-Rong Zhang,Donghai Mei

Electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) offers a sustainable route for biomass valorization. The technoeconomic viability of this promising route, however, hinges on developing efficient electrocatalysts. Moving beyond conventional structural engineering of catalysts, we introduce a surface modification strategy using a small amount of hydrophobic ionic liquids (ILs) to adjust the local electrochemical microenvironment. Specifically, by modifying a porous conductive metal organic framework (Ni-HHTP) with [MTBD][NTf 2 ], the FDCA yield and Faradaic efficiency (FE) are significantly enhanced to 99.9% and 97.0%, respectively, along with a threefold increase in FDCA production rate compared to the unmodified catalyst. Mechanistic studies reveal that the ILs facilitate HMF enrichment at the catalyst surface while preventing water-induced blockage of active sites. This work highlights the transformative potential of interfacial engineering with ILs as a versatile strategy for advancing electrocatalytic systems in biomass conversion applications.

研究领域: 电化学 · 催化 · 生物质转化 · 材料科学 · 绿色化学
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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2021 · IF 3.171

Fabricating amide functional group modified hyper-cross-linked adsorption resin with enhanced adsorption and recognition performance for 5-hydroxymethylfurfural adsorption via simple one-step

Lei Hu,Shunhui Tao,Junting Xian,Xiaodong Zhang,Yao Liu,Xiaojie Zheng,Xiaoqing Lin

In this study, three kinds of amide functional group modified hyper-cross-linked adsorption resin were synthesized by alternating radical copolymerization in simple one-step and applied for 5-hydroxymethylfurfural (5-HMF) adsorption. The successful synthesis and properties of adsorbents were evaluated with Fourier transform infrared spectroscopy, scanning electron microscopy, nitrogen adsorption–desorption isotherms, thermogravimetric analysis, and elemental analysis. Poly ( N , N ′-4,4′-diphenylmethane-bismaleimide-alt-divinylbenzene) (poly (BDM-alt-DVB)) resin exhibited highest adsorption capacity for 5-HMF (64.0 mg·g −1 wet resin) and excellent adsorption selectivity ( α 5-HMF/LA  = 2.71 ± 0.12, α 5-HMF/FA  = 13.88 ± 0.15, α 5-HMF/Glucose  = 11.91 ± 1.11) in the multi-component solution at 25 °C. Langmuir isotherm model well fitted the equilibrium adsorption data within the initial 5-HMF concentration range of 0.5–10.0 g·L −1 with highest correlation coefficient. Furthermore, the thermodynamic parameters demonstrated that the adsorption of 5-HMF onto poly (BDM-alt-DVB) resin was spontaneous and exothermic. Kinetic study revealed that the adsorption process was fast, reaching equilibrium within 12 min. Importantly, the poly (BDM-alt-DVB) resin also demonstrated excellent reusability. In summary, the poly (BDM-alt-DVB) resin will be useful in 5-HMF hydrolysate separation applications.

研究领域: 化学工程 · 材料科学 · 环境科学
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NEW JOURNAL OF CHEMISTRY · 2023 ·Vol. 47 ·期 39 ·18450-18460 · IF 3.3

Efficient conversion of glucose to 5-hydroxymethylfurfural by multi-functionalized γ-Al2O3 beads

Yao Shen,Fang Lin,Kang Wang,Xitao Wang

CaO-doped γ-Al2O3 beads were prepared by an alginate assisted sol–gel method, followed by grafting with alkyl groups and impregnation of NbCl5 to construct multi-functionalized γ-Al2O3 beads for efficient catalytic conversion of glucose to 5-hydroxymethylfurfural (5-HMF). Doping with CaO improved the binding capacity of the catalyst with glucose and increased the Lewis acid amount. However, a high CaO content would cover the Lewis acid sites of γ-Al2O3, resulting in a lower isomeric conversion of glucose to fructose. When the C8–Ca(10%)–γ-Al2O3 catalyst was loaded with Nb2O5, intermediate fructose was consumed rapidly resulting in complete conversion of glucose, which indicated that conversion of glucose to 5-HMF involved the isomeric conversion of glucose to fructose followed by dehydration of fructose to 5-HMF. This was necessary to balance hydrophilic isomerization reactions with restraining the rehydration of 5-HMF by hydrophobic modification. This is similar to the reaction in which a medium with a certain amount of water was beneficial for glucose isomerization. Under the synergistic effect of Lewis acid provided by γ-Al2O3 and Brønsted acid offered by Nb2O5, C8–Ca(10%)–γ-Al2O3–Nb(3%), a glucose conversation rate of 100% and the highest yield of 5-HMF (68.4%) were achieved in the reaction medium with a dimethylsulfoxide/H2O (V/V) ratio of 4 : 1, a catalyst amount of 33 mg, a reaction temperature of 140 °C and a reaction time of 4 h.

CAS / MDL: 50-99-7 10026-12-7
研究领域: 化学工程 · 催化 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Synthesis of bifunctional tin-based silica–carbon catalysts, Sn/KIT-1/C, with tunable acid sites for the catalytic transformation of glucose into 5-hydroxymethylfurfural

Armin Rezayan,Ke Wang,Renfeng Nie,Tianliang Lu,Jianshe Wang,Yongsheng Zhang,Chunbao Charles Xu

Catalytic transformation of carbohydrates to bio-chemicals such as 5-Hydroxymethylfurfural (HMF) has become a hot research topic, but development of cost-effective/efficient catalysts and processes remains a challenge for industrial application. In this study, efficient bifunctional Sn/KIT-1/C catalysts with controllable acid sites were synthesized and applied for glucose-to-HMF conversion. Strong Lewis acid sites were introduced into the framework of disordered mesoporous silica by liquid-phase grafting of tin chloride, and Bronsted acid sites were generated by inserting carbon into the mesopores, followed by controlled oxidation of the carbon. Characterizations revealed that optimizing the amount of carbon source, and carbonization and oxidation temperature provided a proper amount and strength of acidity that could significantly catalyze glucose dehydration reaction to HMF with suppressed byproducts formation. The best catalyst Sn/KIT-1/C(75–400-300) demonstrated superior catalytic performance at 175 °C for 2 h under THF/H 2 O biphasic system, obtaining 78.4 ± 2.1% and 82.9 ± 2.4% HMF yield and selectivity, respectively. The high activity may be attributed to catalyst high surface area/porosity, and the presence of well-balanced amounts and strength of Lewis/Bronsted acid sites. The catalyst could maintain its excellent catalytic activity for five consecutive runs, suggesting the high physical–chemical stability of the catalyst. The results obtained in this work demonstrated that bifunctional metal-supported silica–carbon composites can be a promising catalyst for simple/complex carbohydrates conversion to HMF/bio-based chemicals.

研究领域: 催化 · 化学工程 · 材料科学 · 生物化学
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ChemSusChem · 2024 · IF 7.5

Ultra-Dilute SnCl4-Catalyzed Conversion of Concentrated Glucose to 5-Hydroxymethylfurfural in Aqueous Deep Eutectic Solvent

Guo Xusheng,Qin Chuan,Si Yuxi,Lyu Xilei,Youwei Cheng

5-Hydroxymethylfurfural(HMF) is a versatile chemical synthesized from glucose dehydration catalyzed by metal chloride (MClx) in deep eutectic solvents (DESs). However, the low glucose concentration and high catalyst dosage hinder large-scale HMF production. Herein, we report an aqueous DES of tetraethylammonium bromide(TEAB)-glucose for converting concentrated glucose (40 wt%, relative to TEAB) using ultra-dilute SnCl4 (0.25 mol%), achieving a 62% yield of HMF. Ultra-dilute MClx-catalyzed selective conversion of glucose is feasible only when combining SnCl4 with Br-based DES, which is elucidated by density functional theory and molecular dynamic calculations. Using SnCl4 is essential due to its higher glucose isomerization activity than AlCl3 and CrCl3, which can be attributed to its low-barrier coordination with glucose and its barrier-free separation from fructose. Halide anions in DESs strongly interact with glucose, hindering the MClx-glucose coordination and thereby reducing MClx’s activity for glucose isomerization. Consequently, Br-based DESs facilitate higher activity of MClx than Cl-based DESs, due to the weaker interaction between halide anion and glucose. In addition, we elucidated the side reactions including condensation, polymerization, and isomerization, and proposed a reaction network. Our findings clarify the differential activity of MClx and the impact of halide anions in DESs on MClx’s activity.

CAS / MDL: 10060-12-5 50-99-7
研究领域: 化学工程 · 催化 · 绿色化学 · 材料科学 · 计算化学
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Sustainable Energy & Fuels · 2022 ·Vol. 6 ·期 23 ·5281-5289 · IF 6.813

Complementary metal–semiconductor interactions on Ag-TiO2 NT heterojunction for the efficient electrochemical reduction of 5-hydroxymethylfurfural

Zhefei Zhao,Xingyu Luo,Jiaxi Peng,Siqi Wang,Tianyang Guo,Huajun Zheng

Electrocatalytic conversion of biomass-derived platform molecules is regarded as an emerging approach to obtain high-value fuels and chemicals. Herein, a heterostructured design strategy involving dispersed Ag nanoparticles immobilized on one-dimensional TiO2 nanotubes (Ag-TiO2 NTs) for the electroreduction of 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF) was reported. The optimal electrode exhibited an 82.2% FE, 89.8% selectivity, and DHMF productivity value of 0.1 mmol cm−2 h−1. Electrochemical measurements combined with density functional theory (DFT) calculations manifested that the superior performance was derived from the heterojunction-induced metal–semiconductor interactions at the interface, by which the TiO2 NTs and Ag bring complementary advantages inhibiting the hydrogen evolution reaction (HER) and facilitating charge transfer. Moreover, the catalytic activity of the Ag sites on Ag-TiO2 NTs was considered separately. The mass activity of Ag on Ag-TiO2 NTs reached 5.8 mol L−1 g−1, which was far more than that of Ag mesh (0.038 mol L−1 g−1), indicating the significantly enhanced activity of Ag with high utilization. This could be attributed to the controllable nucleation of Ag through the confinement effect of TiO2 NTs, acquiring dispersed Ag nanoparticles. The design scheme for the heterostructured Ag-TiO2 NTs electrocatalyst displays prospective applications for developing highly efficient electrocatalysts for the electrochemical reduction of HMF.

研究领域: 电化学 · 材料科学 · 催化 · 纳米技术
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2024 · IF 5.9

Conversion of biomass-derived carbohydrates into 5-hydroxymethylfurfural over sulfonated zirconium/tin mixed-metal metal–organic frameworks in deep eutectic solvents-water based biphasic system

Chenxi Lu,Bingqing Hu,Liangzhi Li,Xin Ju,Lishi Yan

5-hydroxymethylfurfural (5-HMF) is a key platform chemical that can be applied to generate varied value-added products. Herein, the sulfonated zirconium/tin Mixed-Metal metal–organic frameworks (MOFs), Sn/UiO-66-SO 3 H catalysts were employed for catalytic conversion of biomass-derived carbohydrates (glucose, sucrose, maltose, starch, and cellulose) to 5-HMF in green deep eutectic solvents (DESs)-water based biphasic system. The Sn/UiO-66-SO 3 H catalysts were prepared by infiltrating Sn 4+ into the UiO-66-SO 3 H via post-synthesis modification. The synthesized catalysts were characterized by PXRD, SEM, FTIR, N 2 adsorption–desorption analysis, XPS, ICP-OES, NH 3 -TPD and Py-FTIR. The synergistic effect of Zr 4+ and Sn 4+ increased the total acidity and pore size of MOFs, thus promoting the catalytic performance of MOFs towards carbohydrates conversion to 5-HMF. The 24-Sn/UiO-66-SO 3 H with impregnation of Sn 4+ for 24 h presented desired catalytic ability, which resulted in 81.5 % and 41.7 % 5-HMF yields from glucose and cellulose in DES betaine-malic acid–water/MIBK biphasic system, respectively. Moreover, the five-recycling test for 24-Sn/UiO-66-SO 3 H demonstrated excellent reusability of the prepared catalyst. This study offered a novel sulfonated Mixed-Metal strategy on MOFs in DES betaine-malic acid–water based biphasic system for the production of 5-HMF from biomass-derived carbohydrates.

研究领域: 催化 · 绿色化学 · 材料科学 · 生物质转化 · 化工工程
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2025 · IF 6.2

Efficient Production of Mano/Xylo-Oligosaccharides with Excellent Probiotic Activity through Coupling Catalysis

Yuejie Qiu,Longbin Li,Leping Zhang,Jianxin Jiang,Liwei Zhu

This study develops a catalytic system using pyruvic acid (PYA) and Fe2+ to efficiently coproduce xylo-oligosaccharides (XOS) and (manno-oligosaccharides) MOS from food material (Gleditsia sinensis Lam. fruit.) and its waste peel, respectively. The system achieved maximum yields of 67.12% XOS and 57.32% MOS without toxic byproducts such as furfural and 5-hydroxymethylfurfural (5-HMF) below 130 °C. The process employs a two-stage mechanism, where PYA cleaves galactose side chains and xylan backbones, while Fe2+ stabilizes β-1,4-glycosidic bonds, resulting in polymerization degree ratios of X2–3/X4–5 at 0.975 and M2–3/M4–5 at 0.96. The composite oligosaccharides, PFMX, showed significant prebiotic effects, enhancing Bifidobacterium adolescentis growth to 3.4 × 108 CFU/mL─144% higher than commercial fructooligosaccharides (FOS). The concentration of short-chain fatty acids (SCFAs) was 15.09 g/L, with specific products propionic acid (1.44 g/L) and butyric acid (0.15 g/L). PFMX effectively regulates substrate utilization and SCFA metabolism, offering a promising strategy for developing functional foods that target gut inflammation.

研究领域: 催化化学 · 碳水化合物化学 · 食品科学与技术 · 益生元与肠道微生物 · 绿色化学 · 生物炼制
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ChemCatChem · 2016 ·Vol. 8 ·期 23 ·3636-3643 · IF 4.724

Efficient Aerobic Oxidation of 5-Hydroxymethylfurfural in Aqueous Media with Au–Pd Supported on Zinc Hydroxycarbonate

Zhenyou Gui,Wenrong Cao,Shunmugavel Saravanamurugan,Anders Riisager,Lifang Chen,Zhiwen Qi

Graphical Efficient noble alloy : Au–Pd supported on zinc hydroxycarbonate (ZOC) catalysts shows high activity for 5-hydroxymethylfurfural oxidation. The basicity of ZOC can play a crucial role in enhancing the yield of FDCA. Moreover, Au–Pd/ZOC can be recycled at least six times without significant loss of its activity. Bimetallic catalysts with Au–Pd supported on zinc hydroxycarbonate (ZOC) were synthesized by a simple deposition–precipitation method and analyzed by transmission electron microscopy to have a narrow-size distribution of predominantly 1–2 nm. The prepared Au–Pd/ZOC catalysts exhibited excellent activity towards 5-hydoxymethylfurfural (HMF) oxidation in water in the presence of the base NaHCO 3 at benign conditions of 80 °C and 3 bar O 2 , resulting in quantitative yield of 2,5-furandicarboxylic acid (FDCA). The addition of base not only enhanced the yield of FDCA but also stabilized the support ZOC by preventing ZOC from the reaction with formed carboxylic acid intermediates/products, thus allowing Au–Pd/ZOC to be recycled for at least six times without significant loss of activity. The basicity of ZOC could play an important role in obtaining the improved yield of FDCA as compared to other supports.

研究领域: 催化化学 · 绿色化学 · 化学工程 · 材料科学 · 有机合成 · 环境科学
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JOURNAL OF FOOD PROCESSING AND PRESERVATION · 2022 ·Vol. 46 ·期 5 ·e16550 · IF 2.609

Analysis of volatile organic compounds in black garlic made of garlic bulbs after harvesting blanched garlic leaves at different growth periods based on PCA and headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS)

Zhen Liu,Da-Cheng Kang,Xin-Rui Li,Ling-Xiao Liu,Yun-Guo Liu

In this study, garlic bulbs after harvesting blanched garlic leaves at four different growth periods were used as the main experimental objects, and black garlic was prepared by solid-state fermentation at variable temperatures. The volatile organic compounds and flavor fingerprints of black garlic were analyzed by headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS), and the differences of volatile organic compounds in black garlic were compared by principal component analysis (PCA). The physical and chemical indexes of black garlic changed slightly. As the Maillard reaction went on more thoroughly, the content of 5- HMF in black garlic increased. GC-IMS provided information on the characteristics and intensity of 55 volatile organic compounds (monomers and dimers). The results showed that the relative content of organosulfur compounds in black garlic decreased gradually with the extension of the garlic bulb growth period, which was due to the inherent instability of the organosulfur compounds and more complex compounds being formed as precursors in further reactions. The results by PCA showed that BG0 samples can be well distinguished from BG20 samples. Novelty impact statement In this study, garlic bulbs after harvesting blanched garlic leaves at four different growth periods were used as the main experimental objects, and black garlic was prepared by solid-state fermentation at variable temperatures. The volatile organic compounds and flavor fingerprints of black garlic were analyzed by headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS), and the differences of volatile organic compounds in black garlic were compared by principal component analysis (PCA).

CAS / MDL: 67-56-1
研究领域: 食品科学 · 分析化学 · 农业科学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2022 · IF 4.326

Efficient Selective Oxidation of 5-Hydroxymethylfurfural with Oxygen over a ZnCrAl Mixed Oxide Catalyst Derived from Hydrotalcite-like Precursor

Yingying Li,Xueli Ma,Wei Lv,Hong Chen,Linhao Yu,Zewei Ma,Sen Wang,Yongdan Li

Cr-doped ZnAl mixed oxide catalysts (Zn0.75CrAl-x-c) were obtained via calcining the Zn0.75CrAl-x hydrotalcite precursors and were applied in the selective oxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-furandicarboxylic acid (FDCA). Cr doping significantly enhanced the catalytic activity. A 95.1% 5-HMF conversion with an 88.1% FDCA selectivity was achieved over the Zn0.75CrAl-6-c catalyst at 130 °C under 0.6 MPa oxygen for 4 h. The good performance was associated with the high specific surface area and high oxygen vacancy concentration. Moreover, the Zn0.75CrAl-6-c catalyst was used for five cycles without a significant activity loss indicating excellent stability.

研究领域: 催化 · 化学工程 · 材料科学
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FOOD RESEARCH INTERNATIONAL · 2023 · IF 8.1

Exploring correlations between green coffee bean components and thermal contaminants in roasted coffee beans

Ruihong Dong,Mengting Zhu,You Long,Qiang Yu,Chang Li,Jianhua Xie,Yousheng Huang,Yi Chen

This study evaluated chemical compositions of green coffee beans from multi-production regions and correlated this information with thermal contaminants in roasted coffee. Using multivariate statistical techniques, formation of 5-hydroxymethylfurfural (5-HMF), furan, 2- and 3-methylfuran were positively correlated with lipid, sucrose, glutamic acid, phenylalanine, margaric acid, linolenic acid and trigonelline in green coffee beans. Moreover, significant positive correlations between acrylamide (AA) levels with aspartic acid, serine, alanine, histidine, asparagine, protein, and caffeine was found in green beans. Despite this, 5-HMF, furan, 2- and 3-methylfuran showed negative correlations with active constitutes (neochlorogenic acid, cryptochlorogenic acid, caffeine, total phenolics (TPC) and total flavonoids contents (TFC)), and several amino acids, and there were slight negative relationships between AA and myristic acid, palmitic acid, chlorogenic acid, sucrose, lipid, TPC and TFC. This study provides valuable enlightenment for the selection of proper coffee beans for production of coffee with high nutrition and low chemical hazardous risks.

CAS / MDL: 149-91-7
研究领域: 食品科学 · 分析化学 · 营养学
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