CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Wangjie Chu,Shengkai Ke,Kexin Feng,Weizhen Xie,Zecui Sheng,Lu Lin,Xing Tang
Base-regulated ROS strategy enables mild HMF-to-FDCA oxidation. • NaHCO 3 stabilizes ·O 2 − ; NaOH promotes ·O 2 − /·OH synergy. • NaOH system drives O 2 relay: O 2 → ·O 2 − → H 2 O 2 → ·OH for FDCA synthesis. The sustainable conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) via aerobic oxidation is a cornerstone of future biorefinery, yet its practical implementation under mild conditions is constrained by the spin-forbidden activation of triplet O 2 . In this work, we report a base-regulated reactive oxygen species (ROS) strategy that enables efficient HMF oxidation to FDCA at low temperatures (30–60 °C) under ambient oxygen pressure. We find that weak base NaHCO 3 selectively stabilizes ·O 2 − , directing a selective oxidation pathway, whereas strong base NaOH promotes a synergistic ·O 2 − /·OH mechanism that substantially accelerates the overall reaction. Through careful optimization, a 95.8% FDCA yield is obtained under ambient O 2 flow. Kinetic analysis, including reaction order determination and kinetic isotope effect measurements, demonstrates that O 2 activation is the rate-limiting step in the NaOH system, following a relay activation pathway of O 2 → ·O 2 − → H 2 O 2 → ·OH. This work not only elucidates the mechanistic role of bases in regulating ROS during HMF oxidation but also provides a practical and green route for synthesizing FDCA under mild, ambient-pressure conditions, advancing the field of sustainable biomass conversion. This work demonstrates a base-regulated reactive oxygen species (ROS) strategy for the mild oxidation of HMF to FDCA. The weak base NaHCO 3 selectively stabilizes ·O 2 − , directing a selective oxidation pathway, whereas the strong base NaOH promotes synergistic ·O 2 − /·OH participation, substantially accelerating the reaction. Mechanistic studies reveal that O 2 activation follows a relay pathway: O 2 → ·O 2 − → H 2 O 2 → ·OH in the NaOH system. Under ambient oxygen pressure and at 30–60 °C, a 95.8% FDCA yield is achieved, offering a new route for green biomass conversion. Download: Download high-res image (47KB) Download: Download full-size image
✓ 已验证
DOI
高影响因子
MOLECULES
·
2020
·Vol. 25
·期 11
·2475
·
IF 3.267
Yanliang Yang,Dexi Yang,Chi Zhang,Min Zheng,Ying Duan
The development of a simple and durable catalytic system for the production of chemicals from a high concentration of a substrate is important for biomass conversion. In this manuscript, 5-hydroxymethylfurfural (HMF) was converted to 1-hydroxy-2,5-hexanedione (HHD) using the combination of commercial Pd/C and acetic acid (AcOH) in water. The influence of temperature, H2pressure, reaction time, catalyst amount and the concentration of AcOH and HMF on this transformation was investigated. A 68% yield of HHD was able to be obtained from HMF at a 13.6 wt% aqueous solution with a 98% conversion of HMF. The resinification of intermediates on the catalyst was characterized to be the main reason for the deactivation of Pd/C. The reusability of the used Pd/C was studied to find that most of the activity could be recovered by being washed in hot tetrahydrofuran.Keywords:HMF;1-hydroxy-2,5-hexanedione;acetic acid;Pd/C;high concentration
研究领域:
化学工程
·
生物质转化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 26
·19823-19829
·
IF 3.84
Zhenzhen Miao,Tianxiao Wu,Jingwei Li,Ting Yi,Yibo Zhang,Xiangguang Yang
The oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) was efficiently catalyzed when Pt nanoparticles (NPs) were supported onto a Ce0.8Bi0.2O2−δ solid solution. 98% yield of FDCA was achieved within 30 min at room temperature and the catalyst was reused five times without much loss of FDCA selectivity. It is the first report on the oxidation of HMF, an alcohol and an aldehyde, effectively catalyzed by a ceria-based material supported Pt catalyst. The individual properties of the Pt NPs and the ceria-based support were retained and not affected after their combination. The superior oxygen activation ability of the Bi-doped ceria thoroughly changed the performance of the ceria supported Pt catalyst. Pt NPs were responsible for the formation of the Pt–alkoxide intermediate, followed by β-H elimination with the help of hydroxide ions. Bi-containing ceria accelerated the oxygen reduction process because of the presence of a large amount of oxygen vacancies and the cleavage of the peroxide intermediate promoted by bismuth. These specific functions were well incorporated during the catalytic oxidation cycle, leading to the generation of the highly efficient Pt/Ce0.8Bi0.2O2−δ catalyst for HMF oxidation at room temperature.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
CELLULOSE
·
2020
·Vol. 27
·期 6
·3037-3054
·
IF 4.21
Zhang Yunlei,Li Bing,Guan Wen,Wei Yanan,Yan Changhao,Meng Minjia,Pan Jianming,Yan Yongsheng
Nitrogen-doped carbon materials have attracted enormous interest in catalysis owing to their outstanding catalytic performance. In this work, nitrogen-doped carbonaceous catalysts (NCC) supported on inexpensive and naturally abundant halloysite nanotubes were successfully synthesized via precipitation polymerization, calcination, and sulfonation processes. The physical and chemical properties of the obtained catalysts were systematically characterized by different methods. The results indicated that NCC catalysts had mesoporous structures, excellent thermostability and acid-base bi-functional active sites. One-pot synthesis of 5-hydroxymethylfurfural (HMF) from glucose was performed to investigate the synthesized NCC catalysts. Benefiting from the synergistic effects of the acid-base bi-functional active sites, the highest HMF yield (62.8%) was achieved in an isopropanol-mediated DMSO system under optimal conditions. Moderate to excellent yields of HMF were also obtained from one-pot conversions of other carbohydrates, including inulin, sucrose, cellobiose, maltose and starch, with our developed catalytic system. The one-pot production of HMF from cellulose was also smoothly processed by the NCC bi-functional catalyst in an IL-based system. This work has developed a versatile strategy for designing nitrogen-doped carbonaceous catalysts that can be employed for the direct transformation of renewable carbohydrates to platform chemicals.
研究领域:
催化化学
·
材料科学
·
可再生资源化学
✓ 已验证
产品关联
DOI
高影响因子
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
·
2022
·
IF 4.831
Juanhua Zhang,Yuzhen Li,Mengxiao Lv,Yihui Bai,Zhenmin Liu,Xuexiang Weng,Chunping You
5-Hydroxymethylfurfural (5-HMF) is a useful indicator of thermal damage degree and freshness of milk. It is of great importance to develop simple, rapid and accurate analytical methods for the sensitive detection of 5-HMF in milk and milk-based products. In this work, surface-enhance Raman spectroscopy (SERS) was used for rapid determination of 5-HMF in processed cheese by colloidal Au nanoparticles (AuNPs) substrate synthesized by the classical solvothermal reduction method. Density functional theory (DFT) calculations were carried out to determine the vibration assignments of 5-HMF and the surface enhancement effect of AuNPs substrate. The results found that a good linear response on the AuNPs substrate for 5-HMF in the concentration range of 0.1–75 mM was established with the detection limit of 75 μM (S/N = 3). Furthermore, the present method could be applied to the determination of 5-HMF in a cheese real sample which revealed its promising application in food safety and analysis.
研究领域:
食品安全
·
分析化学
·
食品科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
AICHE JOURNAL
·
2024
·
IF 3.5
Yanru Zhu,Zhen Zhang,Yunfei Zou,Jian Zhang,Zhe An,Xin Shu,Hongyan Song,Jing He
Catalytic conversion of biomass-derived 5-(hydroxymethyl)furfural (5-HMF) into carbon-increased hydrocarbons as drop-in energy-rich biofuels has received a great deal of concern for the development of sustainable chemical industry. Here, we demonstrate a one-pot conversion of 5-HMF into C 9 -alkanes on one single catalyst, acidic–basic layered double oxides (Mg(Al)(Zr)O) supported CuCo alloy. The well-defined multifunctional catalytic sites with harmonious combination carry out cascade catalysis, affording C 9 -alkanes (including 30% of more value-added branched-cycloalkanes) in 83% yield. The basic–acidic sites on Mg(Al)(Zr)O show high activity for aldol condensation of 5-HMF and acetone, producing 4-[5-(hydroxymethyl)-2-furanyl]-3-buten-2-one (HAc) in a yield of >99%. The engineered Co–Cu–Co linkages on supported CuCo perform efficient hydrodeoxygenation, affording C 9 -alkanes in a selectivity of 96% from HAc. C 9 -cycloalkanes are generated from the cyclization of the corresponding monohydric alcohol intermediates by the synergy of acidic and CuCo sites in the hydrodeoxygenation reaction.
研究领域:
化学工程
·
催化
·
可再生能源
·
生物质转化
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2019
·
IF 5.162
Mao Wen,Xue-Ying Zhang,Min-Hua Zong,Ning Li
Furan carboxylic acids are important building blocks in polymer and fine chemical industries. In this work, a simple substrate adaptation strategy was applied to improve the catalytic performances of Comamonas testosteroni SC1588 cells for the synthesis of various furan carboxylic acids. It was found that biocatalytic synthesis of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) was substantially promoted by adding histidine and increasing cell concentrations. HMFCA was produced in a quantitative yield from 200 mM HMF in 24 h. Besides, the HMFCA yields of 71%–81% were achieved with the substrate concentrations up to 250–300 mM. It was firstly found that 4-tert-butylcatechol (TBC), as the stabilizer present in HMF, exerted a significantly detrimental effect on whole-cell catalytic synthesis of HMFCA at high substrate concentrations (more than 130 mM). In addition, a variety of furan carboxylic acids such as 2-furoic acid, 5-methyl-2-furancarboxylic acid and 5-methoxymethyl-2-furancarboxylic acid were synthesized with the yields up to 98%.
研究领域:
生物技术
·
化学工程
·
有机化学
✓ 已验证
产品关联
DOI
高影响因子
ChemSusChem
·
2013
·Vol. 6
·期 5
·820-825
·
IF 7.475
Qingbin Wu,Yani Yan,Qian Zhang,Jinhua Lu,Zhijian Yang,Yahong Zhang,Yi Tang
Graphical Between the sheets: A simple and efficient microwave-assisted HNb 3 O 8 catalytic process is proposed for the dehydration of carbohydrates in a sustainable pure aqueous system, in which the fast in situ exfoliation of the layered HNb 3 O 8 under microwave irradiation is crucial for the remarkable catalytic performance. A simple and efficient microwave-assisted HNb 3 O 8 catalytic process is proposed for the dehydration of carbohydrates in the aqueous phase. A 5-hydroxymethylfurfural (HMF) yield of 55.9 % was achieved at a high substrate/catalyst weight ratio of 50 from a 10 wt % fructose solution, which is close to the yield achieved by homogeneous aqueous systems. The critical factor for this performance is the fast in situ exfoliation of layered HNb 3 O 8 with the aid of microwave irradiation, which leads to quasi-homogeneous catalytic behavior. Importantly, the catalytic system is also applicable for the one-pot production of HMF from di- and polysaccharides, such as inulin, through a consecutive hydrolysis–dehydration reaction. Additionally, the unique restacking feature of the exfoliated HNb 3 O 8 ensures the good reusability of the catalyst.
研究领域:
化学工程
·
催化科学
·
可再生能源
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Analytical Methods
·
2019
·Vol. 11
·期 37
·4835-4841
·
IF 2.378
Wenbin Chen,Siyuan Wu,Jianing Zhang,Fengjie Yu,Xiaoqing Miao,Xijuan Tu
5-Hydroxymethylfurfural (HMF) is an important index for evaluating the quality of honey. In the present study, the recovery of HMF via the salting-out-assisted liquid–liquid extraction (SALLE) was systematically investigated to develop a simple, rapid, and effective method for the determination of HMF in honey. Results indicated that at the concentration of 70 : 30 (acetonitrile : H2O, v/v), sodium carbonate showed the best recovery of HMF from honey with the 0.5 g addition amount of salt. Compared with two other homogenous liquid–liquid extraction methods, i.e. subzero temperature-assisted liquid–liquid extraction and hydrophobic solvent-assisted liquid–liquid extraction, SALLE showed an advantage of higher recovery for HMF. In addition, fructose and glucose were analyzed to investigate the residue of sugars in the extractive. Results demonstrated that the SALLE method could dramatically reduce the residual contents of these two sugars. In addition, SALLE showed the advantages of less consumption of samples and extraction solvents. Finally, the developed method was fully validated and applied for real honey samples. The analysis results obtained using the present method were comparable to those obtained using the official method; this indicated that the proposed method could be used as an alternative method for the routine quality control of HMF in honey.
研究领域:
分析化学
·
食品科学
·
化工
✓ 已验证
产品关联
DOI
高影响因子
BIORESOURCE TECHNOLOGY
·
2022
·
IF 11.889
Xiheng Kang,Jian Peng,Arthur J. Ragauskas,Xiaofei Ren,Chuanling Si,Shuangfei Wang,Xueping Song
The complexity of polysaccharide hydrothermal products increases the difficulty of exploring the formation of biochar, limiting the development of biochar. This work clarifies the completive effects of glucan’s main hydrolysates on biochar formation from three aspects: experimental, thermodynamic, and kinetic. The products distribution illustrates that 5-HMF, FA, and LA are mainly involved in the formation of biochar. Biochar mainly includes furan ring, ether group, and ester group by the analysis of magic-angle-spinning nuclear magnetic resonance, X-ray photoelectron spectroscopy, and elemental analysis. Combined experiments and density functional theory analysis, the etherification reaction of 5-HMF itself is most likely to occur and is key to form biochar, followed by the esterification of FA with 5-HMF, and then the etherification of 5-HMF and LA. The further verified experiments also manifest these results. This work will develop a foundation for exploring the complex formation mechanism of cellulose-based biochar.
研究领域:
化学
·
环境科学
·
生物质能
✓ 已验证
DOI
PubMed
高影响因子
ChemSusChem
·
2025
·
IF 6.6
Ao Dong,Chengyang Guo,Shuo Zhang,Yunjin Song,Junwei Ma,Xiaoyan Deng,Hongtao Gao
To improve water splitting efficiency and enhance energy utilization, it is crucial to develop catalysts with excellent activity, long-term stability, and low cost. In this study, we synthesized a three-dimensional nanostructured amorphous CoMoP/NF bifunctional catalyst for both the hydrogen evolution reaction (HER) and the 5-hydroxymethylfurfural oxidation reaction (HMFOR), using a sacrificial template method. Benefiting from element doping regulation and morphology control, CoMoP/NF exhibited outstanding catalytic activity. Notably, in an electrolytic water system coupled with HER and HMFOR, a cell voltage of only 1.5 V was required at a current density of 20 mA cm−2, approximately 189 mV lower than that of a traditional water electrolysis system. This study presents a novel energy-saving method for hydrogen production through the HER/HMFOR electrolysis system.
研究领域:
材料科学
·
能源研究
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CARBOHYDRATE POLYMERS
·
2026
·
IF 13.2
Jinpeng Zhai,Chao Liu,Lijuan Sun,Beichen Xue,Yongxin Wu,Rui Xiao
Biomass-derived carbohydrates, as abundant and renewable feedstocks, hold great promise for producing porous carbon materials (PCMs) applicable in CO 2 capture and syngas purification. This study presents a novel strategy for synthesizing N, O-dual doped carbon (NOC) materials through co-pyrolysis using 5-hydroxymethylfurfural (5-HMF) and chitosan (CTS) as precursors, wherein 5-HMF acts as a structural modulator. Combining experimental characterization with density functional theory (DFT) calculations, this work systematically investigated the synergistic mechanism between functional group evolution and carbon framework construction during co-pyrolysis, and elucidated the influence of N, O doping configurations on CO 2 adsorption selectivity. The results indicate that the incorporation of 5-HMF promotes a three-step reaction pathway introducing N, O-containing functional groups such as imine group (C=N) and carbonyl (C=O). The NOC prepared at 800 °C exhibited a CO 2 /H 2 selectivity of 43.4 and a CO 2 /(CO + H 2 ) multicomponent selectivity of 24.4 in a continuous flow (CO 2 /CO/H 2 , 25 °C, 1 bar). Theoretical calculations further revealed that the synergistic coupling of pyridinic N and carbonyl groups on the carbon surface significantly enhances surface polarity and Lewis basicity, thereby strengthening the selective adsorption of polar CO 2 molecules via Lewis acid-base interactions and electrostatic induction.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）