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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2024 · IF 3.8

Selective Conversion of Inulin into 5-Hydroxymethylfurfural and Levulinic Acid in Micropacked Bed Reactors

Ruixue Zhang,Weiyao Yang,Hongda Zhang,Le Sang,Zhiping Zhao

This work presents the efficient, safe, and continuous production of 5-hydroxymethylfurfural (HMF) and levulinic acid (LA) from inulin in micropacked bed reactors (μPBRs) over HND-580. Through optimization reaction conditions, the highly selective production of fructose and LA from aqueous inulin and HMF from an inulin DMSO-water mixed solution can be achieved with respect to other reactor technologies. The highest yields of 89% for fructose, 81% for HMF, and 84% for LA can be obtained within a reaction time of 7.26 min. Polysaccharide inulin is used as the reaction substrate, and the space-time yield (STY) of HMF and LA in μPBRs is at least an order higher than that in conventional batch reactors. Subsequently, an intrinsic kinetic model for inulin conversion is established. The most predicted values show good agreement with the experimental results with a relative error of ±20%.

CAS / MDL: 67-47-0 7439-91-0
研究领域: 化学工程 · 催化 · 生化工程 · 可再生能源
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ENERGY & FUELS · 2023 · IF 5.3

High-Yield Synthesis of 5-Hydroxymethylfurfural from Untreated Wheat Straw Catalyzed by FePO4 and Organic Acid in a Biphasic System

Xu Zhang,Haowen Cui,Qinfang Li,Haian Xia

It is of great significance to develop an affordable and environmentally friendly method for producing 5-hydroxymethylfurfural (HMF) and furfural from inexpensive and abundant agricultural waste. Herein, FePO4 combined with organic acids such as mandelic acid were used as catalysts in a one-pot catalytic conversion of untreated wheat straw into HMF and furfural in a two-phase system of THF/H2O saturated by NaCl. H+, Fe(OH)2+, and Fe(OH)2+ originated from partially dissolved FePO4 in hot water together with organic acids provided Brønsted and Lewis acid sites for the cascade conversion of wheat straw. Whereas organic acid could regulate the concentrations of Lewis and Brønsted acid sites to promote the dehydration process of fructose and hinder the production of by-products and humins, boosting the yield of HMF and furfural. The response surface methodology (RSM) was used to optimize the reaction conditions. The highest yield of HMF was 62.9% at 200 °C and 120 min, which is higher than the reported yield of HMF using lignocellulose as raw material in the current literature. Furfural has also achieved a higher yield (93.9%) at 180 °C and 90 min. This study demonstrates the rationality of the deployment of lignocellulose to produce furan compounds by organic acids and FePO4, providing the possibility for efficient production of HMF and furfural from recalcitrant agricultural waste.

CAS / MDL: 110-16-7
研究领域: 化学工程 · 绿色化学 · 生物炼制 · 可持续化学
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CHEMICAL ENGINEERING SCIENCE · 2022 · IF 4.889

One-pot preparation of CuOx-CoOy heterostructure decorated on graphene for highly efficient oxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-furandicarboxylic acid (FDCA)

Minhui Rao,Mengyu Wang,Xuelin Zheng,Danmei Pan,Congbin Hong,Kaidong Chen,Liangxu Lin

Dense CuO x -CoO y nano-heterostructures were uniformly assembled on the surface of graphene via surfactant induced assembly and hydrolysis with the presence of PVP and NaBH 4 . As-prepared CuO x -CoO y -PVP/G composite exhibited excellent performance for selective oxidation of 5-HMF to FDCA in aqueous solution with NaClO as oxidant at 30 °C, which is comparable to noble metal catalysts. The outstanding performance can be attributed to fascinating synergetic contributions from the CuO x -CoO y heterostructure on graphene substrate, giving improved interfacial contact, increased active sites and accelerated electron transfer process to promote the catalytic reaction. This work provides a high-performing catalyst for oxidation of 5-HMF to FDCA, as well as an ideal design of metal-oxide heterostructures/graphene composite catalysts for more broad applications.

研究领域: 催化 · 材料科学 · 化学工程 · 纳米技术
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CHEMBIOCHEM · 2018 ·Vol. 19 ·期 7 ·654-659 · IF 2.774

Efficient Catalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid by Magnetic Laccase Catalyst

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 · 生物技术 · 绿色化学 · 生物基化学品
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DALTON TRANSACTIONS · 2022 ·Vol. 51 ·期 48 ·18473-18479 · IF 4.569

MIL-47(V)-derived carbon-doped vanadium oxide for selective oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran

Yan Zhou,Shanshan Lv,Han Li,Qikang Wu,Taiyu Chen,Shaohuan Liu,Wanying Li,Wenjuan Yang,Zheng Chen

The development and transformation of biomass-derived platform compounds is a sustainable way to deal with the fossil fuel crisis. 5-Hydroxymethylfurfural (HMF) can be reduced or oxidized to produce many high-value compounds; however, it is challenging to effectively produce 2,5-diformylfuran (DFF) due to overoxidation. In this work, a carbon-doped V2O5 (C–V2O5) material was obtained through pyrolysis of MIL-47(V) nanorods, a typical metal–organic framework material. The X-ray diffraction patterns and X-ray photoelectron spectra showed that the graphitized carbon species were incorporated in C–V2O5. High-efficiency HMF oxidation, high specific selectivity for DFF and excellent recycling could be achieved with the C–V2O5 catalyst. Fourier-transform infrared spectroscopy combined with density functional theory (DFT) calculation revealed that graphitized carbon weakens the VO bond and promotes the formation of oxygen vacancies in C–V2O5, thus improving the catalytic activity in the oxidation of furfuryl alcohols. The V4+ induced by oxygen vacancies will be oxidized by O2 to form V5+, so that the cycle can be realized. It exhibits remarkable selectivity in the oxidation of different alcohols produced from biomass based on the relatively constant active sites in C–V2O5.

CAS / MDL: 7718-98-1
研究领域: 材料科学 · 催化 · 化学工程 · 可持续化学
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Catalysis Science & Technology · 2025 · IF 4.2

Facile Synthesis of SrNb2O6 Nanorods for Enhanced Selective Conversion of Fructose to 5-Hydroxymethylfurfural

Peixin Wang,Ruilong Zhang,Ifunanya Rejoice Akaniro,Puranjan Mishra,Reeti Kumar,Jun Zhao

Catalytic dehydration of fructose to 5-hydroxymethylfurfural (HMF) is a key reaction in biomass valorization and sustainable chemistry. The development of solid acid catalysts with high selectivity for HMF remains challenging due to the formation of undesired by-products, such as levulinic acid and formic acid in the reaction. In this study, SrNb2O6 catalysts with various morphologies were prepared by a facile one-step hydrothermal method, triggering synergetic catalysis for selective transformation of fructose to HMF. Among the Nb-based mixed oxides synthesized under varying conditions, including different pH environments and Nb concentrations, SrNb2O6 nanorods (denoted as SNO-NR, with pH = 13 and Sr/Nb ratio of 1:2) demonstrated the highest catalytic performance. Specifically, it achieved a 74.9% HMF yield and a selectivity of 78.5% in DMSO at 120°C for 1 hour. Comprehensive characterization analyses collectively indicated that an optimal acid capacity and a balanced Brønsted/Lewis acid ratio, which facilitate synergistic effects, are critical for achieving a highly selective conversion of fructose to HMF. Furthermore, it is also noteworthy that this SNO-NR catalyst was recyclable and stable for up to six runs with a minor reduction in its activity, confirming its remarkable robustness.

研究领域: 催化化学 · 可持续化学 · 纳米材料 · 生物质高值化
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NEW JOURNAL OF CHEMISTRY · 2025 · IF 2.5

Efficient hydrogenolysis of 5-hydroxymethylfurfural to produce 2,5-dimethylfuran using unsupported nickel-molybdenum nitride catalysts

Wenpeng Han,Shujuan Wang,Fujiang Geng,Lei Liu,Ruidi Wei,Mingxing Tang

An efficient and selective nickel-molybdenum nitride catalyst has been developed for the hydrogenolysis of 5-hydroxymethylfurfural (HMF) to produce 2,5-dimethylfuran (DMF). The results showed that Ni2Mo3N phase of the catalyst exhibited good hydrogenation activity for HMF, while Ni6Mo6C1.06 phase demonstrated effective C-O bond hydrogenolysis activity. By regulating the Ni/Mo molar ratios, the proportions of the Ni2Mo3N and Ni6Mo6C1.06 phases can be adjusted, and the NiMoNx (Ni:Mo=1:2) catalyst with good performance was prepared. Additionally, 2-propanol, as a good solvent, can react with HMF to form ethers, facilitating easier hydrogenolysis. This method leads to full conversion of HMF, achieving a 99% yield of DMF at 160 oC and 2 MPa H2 for 5 h. Furthermore, the catalyst displayed good recyclability, maintaining its activity over 4 cycles, indicating it has the potential application for the industrialization of 5-HMF hydrogenolysis to produce DMF.

研究领域: 催化 · 化学工程 · 绿色化学 · 有机合成 · 可再生能源 · 材料科学
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Science China-Materials · 2023 ·Vol. 67 ·期 1 ·162-169 · IF 8.1

Customizing the synergy of reactive oxygen species and photoactive charges on Bi2O2CO3/ZnIn2S4 for the selective photooxidation transformation of 5-hydroxymethylfurfural

Yang Bixia,Zhu Mengyao,Jiang Xingpeng,Shao Wenlei,Wang Zhiqi,Yan Jiawei,Zheng Yanting,Zhuang Zanyong,Yu Yan

The photooxidation of renewable bioderivatives into value-added chemicals is highly significant; however, it typically exhibits low selectivity owing to the challenges in controlling the oxidative species and managing the desirable reaction pathways. In this work, we used the Bi 2 O 2 CO 3 /ZnIn 2 S 4 heterostructure, prepared by a CO 2 -mediated solid–solid phase transition, to catalyze the photooxidation of bioderived 5-hydroxymethylfurfural (HMF) into 2,5-diformylfuran (DFF) with a high selectivity of 98.1% and a yield rate of 882.6 µmol g −1 h −1 . The metal carbonate/oxide heterointerface enables the effective transfer of photoactive electrons and holes, optimizes surface oxygen activation, and facilitates the synergy of ·OOH and holes to selectively convert HMF into DFF. The findings unravel how the tailoring and coupling of the electron–hole pairs and reactive oxygen species on heterostructured materials can promote the usage of renewable feedstocks for sustainable development.

研究领域: 光催化 · 环境化学 · 材料科学 · 绿色化学 · 可再生能源
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ENERGY & FUELS · 2019 · IF 3.021

Fenton Reaction-Modified Corn Stover To Produce Value-Added Chemicals by Ultralow Enzyme Hydrolysis and Maleic Acid and Aluminum Chloride Catalytic Conversion

Ming Yang,Caidi Jin,Shuang E,Jianglong Liu,Shen Zhang,Qingyu Liu,Kuichuan Sheng,Ximing Zhang

Fenton reaction has been widely used for pretreatment of lignocellulose with the advantages of simple operation, a rapid reaction rate, and less pollution. In this study, batch and fed-batch Fenton reactions to treat corn stover (CS) for carbohydrate utilization were tested. The composition analyses showed that the batch reaction had a greater degree of removal of holocellulose but fed-batch reactions could preserve more hemicellulose. Ultralow enzyme hydrolysis (1 FPU/g) was used to hydrolyze the Fenton reaction-modified CS, and the yield of glucose resulting from batch reaction was 2.5 times higher than that from the raw CS. Surprisingly, a combined catalyst of maleic acid and aluminum chloride (MAAL) was used to catalyze the modified CS for 5-hydroxymethylfurfural (HMF) and furfural production, and the highest conversion values for cellulose and hemicellulose achieved were 82 and 95%, respectively. Confirmed by a series of characterizations, this study provides clear insight into the Fenton reaction and how it can alter the lignin structure to facilitate holocellulose utilization.

CAS / MDL: 7446-70-0
研究领域: 化学工程 · 生物化学 · 生物技术
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Biomass Conversion and Biorefinery · 2020 ·Vol. 11 ·期 5 ·1931-1941 · IF 2.602

Catalytic production of 5-hydroxymethylfurfural from sucrose and molasses by aluminum chloride in green aqueous γ-valerolactone system

Tian Xiatian,Qi Benkun,Zhang Shaofeng,Luo Jianquan,Wan Yinhua

5-Hydroxymethylfurfural (HMF) is a promising platform chemical for production of value-added chemicals and fuels. Conversion of abundantly available and cheap sucrose for HMF synthesis was systematically investigated in the present study. Results showed that Lewis acid AlCl 3 is effective in catalytic transformation of sucrose. Combining AlCl 3 with different Brønsted acids, no matter whether they were inorganic acids (HCl, H 2 SO 4 , and H 3 PO 4 ) or organic acids (malic acid, succinic acid, and oxalic acid), or variation of ratio of Lewis acid/Brønsted acid represented by AlCl 3 /HCl, did not change the obtained maximum HMF yields compared with AlCl 3 alone, but shortened the time required to reach the maximum HMF yield. Sucrose conversion in a green reaction media of aqueous γ-valerolactone (GVL) solvent resulted into comparable HMF yields with dimethyl sulfoxide (DSMO)-water system. Addition of monovalent salt NaCl and divalent salt Na 2 SO 4 produced opposite effect with Cl − promoting while SO 4 2− inhibiting HMF production. Furthermore, HMF synthesis from constituent monosaccharides of sucrose and molasses, a by-product from sugar manufacturing process, was also carried out and it was found that an equivmole mixture of glucose and fructose gave rise to almost identical HMF yield to the same mole of sucrose. Molasses, even after chemical pretreatment for removal of certain amount of inorganic salts and color substances, was significantly inferior to synthetic molasses in terms of HMF formation, indicating the complexity and difficulty in chemical valorization of molasses for production of platform molecules.

研究领域: 化学工程 · 绿色化学 · 生物化学工程
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Rationally designed Au-ZrOx interaction for boosting 5-hydroxymethylfurfural oxidation

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 · 材料科学 · 化学工程 · 生物质转化
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CELLULOSE · 2023 ·Vol. 30 ·期 12 ·7575-7589 · IF 5.7

A novel strategy for highly efficient conversion of cellulose into 5-hydroxymethylfurfural using green and effective stepwise catalytic systems

Wang Tao,Zhang Cailiang,Feng Hui,Zou Qingjun,Huang Wenrui,Wu Jiacong,Han Juan,Wang Yun

In this study, a green and effective stepwise catalytic system for cellulose conversion to 5-hydroxymethylfurfural (HMF) is reported. In a pretreatment process, very fast (15 min) dissolution of cellulose was achieved at a low temperature of 70 °C, utilizing ZnBr 2 ·4H 2 O as the best dissolution solvent, which to improve the reactivity of cellulase for raw cellulose and increase efficiency of cellulose degradation. Enzyme-inorganic hybrid nanoflowers (Cellulase@β-glucosidase/Zn 3 (PO 4 ) 2 -NF and Glucose isomerase@Zn 3 (PO 4 ) 2 -NF) with different morphological structures were prepared to act as biocatalyst in the sequential conversion of pretreated cellulose to glucose and glucose to fructose. HCl was applied catalyst for dehydration of fructose to 5-HMF in a water/tert-butanol biphasic system. Under optimal reaction conditions, the yield of 5-HMF for the overall reaction from cellulose was about 21.6%. A feasibility route for green conversion of cellulose to 5-HMF is reported. Graphical abstract

研究领域: 化学工程 · 催化 · 绿色化学 · 生物技术
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