INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2026
·Vol. 65
·期 30
·15954-15963
·
IF 3.9
Liu Sijie,Zhao Jinlong,Gao Liya,Ding Xiaoshu,Wang Jiaxi,Zhang Dongsheng,Zhao Xinqiang,Wang Yanji
2,5-Furan dicarboxylic acid (FDCA) is an important biomass
derivative
that is commonly used in the synthesis of green polymers. Currently,
the carboxylation of furoic acid (FA) to produce FDCA requires the
use of large quantities of alkaline reagents to convert FA and CO 2 into carboxylates, followed by the displacement of alkali-metal
ions from the carboxylates using HCl to obtain FDCA. This process
not only involves the use of highly corrosive HCl but also alkaline
reagents that are converted into chlorides after the reaction; the
recovery of these chlorides relies on bipolar membrane electrodialysis
technology. In order to avoid the use of strong acids that corrode
equipment and pollute the environment, eliminate the electrodialysis
process, and directly regenerate alkali metal salts while simplifying
the reaction process, this study has designed a new cyclic process.
The process comprises two steps: (1) under the catalysis of an alkali
metal salt catalyst (Cs 2 CO 3 –CsOPiv/TiO 2 ) supported on spherical titanium dioxide (TiO 2 ) carriers, FA undergoes direct C–H carboxylation to form
the corresponding carboxylate intermediates. (2) Using the green methylation
reagent dimethyl carbonate (DMC), the carboxylate intermediates are
converted in situ to dimethyl furan-2,5-dicarboxylate (FDME), while
simultaneously regenerating the alkali metal salt catalyst component.
Experimental results indicate that the Cs 2 CO 3 –CsOPiv/TiO 2 catalyst achieves a 94% conversion
rate of FA. The generated carboxylate intermediates are completely
converted to FDME with a total yield of 76%.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Xia Jiang,Ziheng Ding,Wenhua Zhang,Zhicheng Jiang,Bi Shi
Electrocatalytic production of 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF) is a sustainable and clean pathway for harvesting both value-added chemicals and green hydrogen (H 2 ). Herein, B, N doped porous carbon supporting Co (Co/BN-C) with abundant pyridinic N-B species was constructed via a one-pot method using chitosan as precursors, which was further applied for the paired electrocatalysis of an HMF oxidation reaction (HMFOR) and H 2 evolution reaction (HER). H 3 BO 4 as a templating agent could increase the specific surface area of the catalyst and expose more active sites for the HMFOR. Meanwhile, H 3 BO 4 also acted as a B source to dope heteroatoms in the carbon matrix, creating surface defects and thus improving electrical conductivity. Besides, B, N-doped carbon substrate induced the electron deficiency of Co nanoparticle, resulting in the strong adsorption of HMF on the catalyst surface via the interactions between the aldehyde group/furan ring of HMF and the catalyst. Consequently, the Co/BN-C catalyst exhibited remarkable performance with a high HMF conversion (> 99%) and selectivity to FDCA (> 98%) and remained high activity after 8 cycles.
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BIOMASS & BIOENERGY
·
2026
·
IF 7
Yahui Zhang,Haowen Cui,Haian Xia
The selective oxidation of furfural (FF) to 2-furoic acid (FA) represents a significant route toward sustainable chemical production. However, existing catalytic systems often suffer from limitations such as low substrate concentrations, harsh reaction conditions, and inadequate selectivity. In this study, a series of Ag/ZrO 2 catalysts with varying Ag loadings were prepared via a deposition–precipitation method and were used for the aerobic oxidation of FF to FA under mild conditions. The effects of metal loading, catalyst mass, reaction temperature, reaction time, and oxygen pressure on FF conversion and FA selectivity were systematically investigated. Under optimized conditions, nearly 100% FA was achieved under 10 wt% FF concentration at low-temperature (ca. 5 °C), while a high selectivity of 90.3% toward FA was maintained even at 20 wt% FF. The catalysts also exhibited excellent recyclability, retaining over 85% FA selectivity after five consecutive cycles. Comprehensive characterization techniques, including XRD, XPS, and HRTEM, were employed to elucidate the structure-activity relationship of the catalysts. The experimental and characterization findings propose a possible reaction mechanism involving synergistic effects of Ag 0 sites for dehydrogenation and ZrO 2 oxygen vacancies for O 2 activation. This work represents a notable advance in the field, as it develops the high efficient catalytic system under high FF concentrations and low-temperature conditions for the first time.
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Journal of Environmental Chemical Engineering
·
2023
·
IF 7.7
Shengnan Zhong,Lina Tian,Lixin Yi,Yifan Liu,Weiguo Cheng,Yibo Wang,Yunong Li
Among various strategies for CO 2 chemical fixation, the CO 2 cycloaddition with epoxides is one of the most promising and efficient approaches, in which ionic liquid (ILs) is a typical relatively environmentally friendly catalyst and medium. However, ILs decomposition and catalytic stability have not been in-depth investigated, and the structure-activity relationship of cations and anions has remained obscure, which would affect the understanding of catalytic behavior and catalyst loss, and limit the theoretical research and industrial application in CO 2 utilization. Therefore, based on a variety of phosphonium ILs we have designed and synthesized for CO 2 cycloaddition, the structure-activity relationship, steric hindrance and electronic effect of various anions and cations have been systematically studied in main and side reactions. Especially, a regulation strategy of cationic flexible steric hindrance and anionic electron effect have been developed to improve both ILs’ activity and stability. Remarkably, the synergistic action of electron-donating effect, hydrogen bond and decreased acidity from flexible steric alkyl groups result in the spatial shielding of cation center and enhancement of the Br's leaving. Consequently, the quaternary phosphonium ILs with asymmetric flexible steric hindrance exhibit the optimal performance, showing propylene oxide (PO) conversion of 99.15% and propylene carbonate (PC) yield of 98.86%, which can efficiently decrease the formation of phosphine oxide, avoiding the decomposition of ILs. This discovery provides a new idea for developing stable and efficient CO 2 fixation system in sustainable industry.
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Biomass Conversion and Biorefinery
·
2023
·
IF 4
Liu Yun,Wang Xueke,Hu Mingyang,Yu Yanyan
2,5-furandicarboxylic acid (FDCA), one of the most important building blocks, has attracted tremendous concerns, and the routes for FDCA synthesis from non-edible hemicellulose are of vital importance from the views of the circular economy. Herein, a multistep process towards hemicellulose-to-FDCA conversion is proposed, including hemicellulose-to-furfural conversion and sequential oxidation to furoic acid (FA), following with cesium furoate (FA-Cs) preparation and its direct carboxylation with carbon dioxide (CO 2 ). The overall conversion yield of the targeted FDCA product towards the hemicellulose-to-FDCA pathway reaches 29.6%. Many efforts are made on the direct carboxylation reaction of FA-Cs with CO 2 using Cs 2 CO 3 as a catalyst. Results show that FDCA with 56.47% yield is achieved via direct carboxylation of FA-Cs at 290 °C for 12 h with 40 mL/min of flowing CO 2 . Different from the previous reports, it is demonstrated that drying methods of FA-Cs show significant effects on the yield and properties of the targeted FDCA product. It is found that the conventional drying method is more suitable than the vacuum drying method. From the putative reaction mechanism, the roles of CO 2 and Cs 2 CO 3 are elucidated. CO 2 plays a direct role in carboxylation reaction, and excessive Cs 2 CO 3 can deteriorate FDCA yield due to the occurrence of decomposition. Interestingly, biochar generated during carboxylation reaction is a promising potential adsorbent, which can efficiently adsorb methylene blue with a removal rate of 96% and an adsorption amount of 80 mg/g. This present work can provide an integrated strategy for both hemicellulose valorization and CO 2 utilization in future.
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BIOCHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 3.9
Siyuan Chang,Bingfeng Li,Tianyi Chen,Leilei Zhang,Yaru Li,Xuejun He,Sen Zhang,Xin Pan
The catalytic transformation of biomass-derived 5-hydroxymethylfurfural (HMF) into value-added chemicals and biofuels has received considerable interest. Previously, we demonstrated that Pseudomonas aeruginosa PC-1 could be used for selective 900 mM HMF oxidation into 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) with over 90% yield. Here, we aimed to mine the potential aldehyde dehydrogenases (ALDHs) for HMF biocatalysis and improved the catalytic activity and tolerance through protein engineering. ALDHs were heterologously expressed in E. coli BL21 (DE3) and subsequently the most efficient HMF oxidation conditions of E. coli /pET -PaALDH70140 were identified. Based on the structural analysis of PaALDH70140 with the HMF and NAD + complexes, the engineering hotspots in the active site architecture were identified and subjected to saturation mutagenesis . The mutant L172R displayed 175% higher HMF catalytic efficiency than PaALDH70140, and the mutant also showed improved HMF-tolerance. Kinetic parameters suggested that L172R had higher HMF affinity and catalytic efficiency, indicating a higher HMF conversion efficiency than the wild-type. Molecular docking revealed that the mutation introduced new hydrogen bonds between the enzyme and HMF, which fixed the spatial position of HMF and shortened the reaction time of the catalysis, thus enhancing the catalytic efficiency of HMF. In the fed-batch process, E. coli /pET -PaALDH70140 - L172R exhibited a 166% increase in the yield of HMFCA within 22 h, proving its potential for HMF bioconversion applications.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Wanying Liang,Guangyue Xu,Yao Fu
A series of metal-TS-1 zeolite catalysts were designed to selectively catalyze the photo oxidation of furfural to C 4 carboxylic acid derivatives at ambient temperature and pressure. The photocatalytic preparation of malic acid from furfural was realized for the first time. The selective distribution of products could be controlled by adjusting the physical and chemical characteristics of the catalyst. Smaller pore size prevented the further conversion of maleic acid to malic acid; moderate acidity was beneficial for the preparation of malic acid; lower valence band was in favor of maleic acid production while higher valence band tended to form malic acid. The synergistic effect of pore structure, acidity and energy band structure of catalysts affected the product distribution. The yield of maleic acid reached as high as 40% over Fe-TS-1, meanwhile, the yield of malic acid reached as high as 63% over Ni-TS-1. The doping of metal was believed to be an effective procedure to adjust the structure and physicochemical properties of zeolite. Matel-TS-1 zeolite was also expected to be widely used in photocatalytic system to achieve more selective reactions.
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CATALYSIS TODAY
·
2023
·
IF 5.3
Zhenyu Li,Enhui Du,Panpan Hao,Liyuan Huai,Yang Zhong,Soliman I. El-Hout,Chunlin Chen,Jian Zhang
The oxidation of biomass-derived 5-hydroxymethyl furfural (HMF) into 2,5-Furandicarboxylic acid (FDCA) is a favorable reaction since FDCA is an ideal alternative to petroleum-based monomer terephthalic acid in bio-based polyester industry. However, producing FDCA with high yield under mild conditions is still challenging, especially at energy-saving near-ambient temperatures. Here, we present a Pd nanoparticles catalyst supported on Vulcan XC-72 carbon (Pd/VC) that can completely convert HMF and achieve an encouraging FDCA yield (92.4%) at 30 ℃. The most important observations include yield declines at pure oxygen bubbling, and the transformation of intermediates becomes stagnant; instead, switching to the diluted oxygen is effectively driving the tandem oxidation as the over-oxidation, and thus, rapid deactivation of the Pd surface could be alleviated. The negative effect of high oxygen concentration also occurs in the dehydrogenation and oxygenation of an extended substrate. Since the decisive influence of oxygen content has often been neglected in past investigations of oxidative transformation over Pd-based catalysts, the current study may offer a critical reminder for other liquid-phase oxidation reactions.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2023
·
IF 8.2
Jingmin Cui,Yan Sun,Linqing Wang,Wenqiang Tan,Zhanyong Guo
In this study, nine chitosan derivatives containing aromatic five-membered heterocycles were prepared and the effects of different grafting methods on the biological activities of chitosan derivatives were investigated. The structures of all the compounds were characterized by Fourier Transform Infrared (FT-IR) spectroscopy and Nuclear Magnetic Resonance (NMR) spectroscopy, while the antioxidant, antifungal and antibacterial activities of the chitosan derivatives were tested. The experimental data suggested that the chitosan derivatives had outstanding inhibitory ability against Fusarium graminearum , Fusarium oxysporum f . sp . cucumbrum , Staphylococcus aureus and Escherichia coli . At the same time, some of the compounds showed strong scavenging ability against DPPH radical and superoxide radical. Cytotoxicity experiments have demonstrated that some chitosan derivatives are non-toxic to L929 cells. More importantly, compared to chitosan, these chitosan derivatives have good water solubility and can be used as potential polymers for antifungal and antibacterial biomaterials in agriculture.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Xinxin Li,Linchuan Cong,Yupeng Wu,Nan Lin,Fangbing Liu,Deyuan Xin,Fuyu Han,Jin Yang,Weitong Chen,Haibo Lin
Electrochemical methods for catalytic furfural conversion have drawn significant interest in both academic and industrial research communities. Paired electrocatalytic conversion has been identified as a promising strategy for reducing energy consumption and promoting carbon neutrality. To optimize product distribution and conversion efficiency, we have developed a divergent paired electrochemical upgrading approach for furfural in acidic environments, with a focus on prioritizing strong gas evolution reactions and product transformations. The high electrocatalytic activity of CuSn/CuF@Cu prepared by electrodeposition can effectively inhibit the hydrogen evolution. The performance of the electrocatalysts and the pathways of electrocatalytic hydrogenation (ECH) of furfural to 2-methylfuran (MF) were investigated by combination of experiments and the density functional theory (DFT) calculations. A stable Ti/PbO 2 electrode with high oxygen evolution overpotential was prepared for anodic electrocatalytic oxidation (ECO) and the product transformation route was described. The conversion of furfural to maleic acid (MA) and MF in acidic environment was successfully achieved. In the paired electrosynthesis system, the electrons generated from anodic ECO of furfural are utilized in valuable and controllable cathodic ECH. It significantly and continuously reduces the power cost associated with renewable energy sources and further promotes the development of biomass electrochemical conversion.
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FUEL
·
2022
·
IF 8.035
Xin Yu,Huiqiang Wang,Wenlong Jia,Chengfeng Li,Jiahong Chen,Lincai Peng,Yong Sun,Xing Tang,Xianhai Zeng,Shuliang Yang,Zheng Li,Feng Xu,Lu Lin
Reduction of high oxidation level furancarboxylic acid (FA) with the retention of the carboxyl group is particularly important for the utilization, however, it has been rarely explored over non-precious catalysts and is challenging. Here, we demonstrate an excellent noble-metal-free trimetallic NiCoAl catalyst for the reductive esterification of FA to methyl 2-tetrahydrofuroate (MeTHFC), which delivers the complete conversion of FA and MeTHFC yield of up to 99%. More importantly, Ni 0.5 Co 0.5 Al could offer Y MeTHFC > 90% over five reusability cycles. Detailed investigations suggest that the high activity originates from the synergistic of Ni-Co alloys sites and acid sites in Ni 0.5 Co 0.5 Al. The Ni-Co alloy sites were mainly responsible for the adsorption and dissociation of H 2 , which in turn improved hydrogenation activity, while the acid sites facilitated the esterification of FA and the adsorption and further activation of the furan ring. This work provides an eco-friendly noble-metal-free catalyst to enrich the strategies for the reductive esterification process.
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RSC Advances
·
2022
·Vol. 12
·期 28
·17990-18003
·
IF 4.036
Wenguang Yu,Xuefeng Gao,Zhicheng Yuan,Haihui Liu,Xuechen Wang,Xingxiang Zhang
The widespread use of graphene as a next-generation material in various applications requires developing an environmentally friendly and efficient method for fabricating functionalized graphene. Chemically, graphene can be used as an electron donor or attractor. Here, graphite was successfully exfoliated, and an in situ Diels–Alder reaction (D–A) was carried out to fabricate functionalized graphene with sole functional groups via mechanochemical ball milling. The reactivities of graphene acting as a diene or a dienophile were investigated. Few-layer (≤2 layers) graphene specimens were obtained by wet ball milling, heating in a nitrogen atmosphere, and solvent ultrasonic treatment. The ball-milling method was more effective than heating in a nitrogen atmosphere, and the [2 + 4] D–A of graphene was more dominant than the [4 + 2] D–A in the ball-milling process. The surface tension of functionalized graphene decreased, which provided a theoretical basis for the dispersion and exfoliation of graphite in a suitable solvent. Functionalized graphene still had a high electrical conductivity, which has far-reaching significance for functionalized graphene to be applied in electronic semiconductors and related applications. Meanwhile, functionalized graphene was applied to polymer composite fibers, the tensile strength and the Young's modulus could reach 780 MPa and 19 GPa. The volume resistivity was two orders of magnitude lower than that of pure fiber. Thus, the use of ball milling to efficiently exfoliate and in situ functionalize graphite will help to develop a strategy that can be widely used to manufacture nanomaterials for various application fields.
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