INORGANIC CHEMISTRY
·
2024
·
IF 4.3
Hongliang Dai,Pengjie Zhou,Shenming Yang,Lili Yang,Hongye Bai,Cui Dai,Guohai Xu,Weiqiang Fan
Electrocatalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is significant for the sustainable production of value-added chemicals. Active sites of catalysts could enhance the activity and selectivity of the HMF oxidation reaction (HMFOR), but the self-healing ability of active sites has been commonly ignored. In this work, Co(OH)2/Ni-MOF was successfully fabricated for efficient oxidation of HMF to FDCA under mild conditions. Electrochemical and cyclic stability experiments demonstrated the high self-healing properties of the dual active sites (Co3+/Ni3+). So, the retention rate of FDCA yield can still reach 98.5%, even after 90 days. HMFOR was further coupled with 4-nitrophenol hydrogenation, which promotes the yield and Faradaic efficiency of FDCA to about 100%. Therefore, this study explores the self-healing properties of species and provides new insights for designing efficient catalysts.
研究领域:
电化学
·
催化
·
可持续化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2021
·
IF 3.764
Xiangbo Song,Jun Yue,Yuting Zhu,Chengyan Wen,Lungang Chen,Qiying Liu,Longlong Ma,Chenguang Wang
Efficient and one-pot conversion of biomass-derived carbohydrate into highly value-added 5-hydroxymethylfurfural (HMF) is a crucial reaction step for the valorization of biomass resources toward bio-based chemicals and fuels. In this work, a series of Sn/SAPO-34 catalysts were prepared through impregnation and evaluated in glucose conversion to HMF. The physicochemical properties of Sn/SAPO-34 catalysts were systematically characterized by SEM, XRD, N2 physisorption, XPS, solid-state 119Sn, 29Si, and 31P NMR, XRF, UV–vis, NH3-TPD, and pyridine-FTIR techniques. It was demonstrated that controlling the Sn loading amount could facilely adjust the acid strength and acid amount of the SAPO-34 zeolite. The incorporation of Sn species could induce the formation of a tetrahedrally coordinated Sn4+ site and Sn-OH site to improve the amounts of Brønsted and Lewis acid sites of the catalyst. However, modification with sufficiently high Sn loading could decrease the acid strength and performance of the catalyst owing to its structure damage. The 5%Sn/SAPO-34 catalyst (i.e., Sn loading calculated based on the mass ratio of SnCl4·5H2O as a precursor to the parent SAPO-34) was found to exhibit the superior catalytic performance under mild conditions and could afford an HMF yield of 64.4% at 98.5% glucose conversion in a biphasic 35 wt % NaCl-H2O/tetrahydrofuran (THF) system at 150 °C within 1.5 h. Additionally, a catalytic reaction pathway was proposed, involving the adsorption of glucose molecules by the −Cl group on the catalyst via a hydrogen bond, followed by glucose isomerization to fructose over the Lewis acid Sn4+ and Al3+ sites and, finally, fructose dehydration to HMF catalyzed by the Brønsted acid Sn-OH and Si-OH-Al sites. The activity of the catalyst decreased due to the leaching of the active site Sn after several consecutive cycles. This work provides insights into the improvement in the Sn-containing zeolite catalyst for tandem conversion of glucose to HMF.
研究领域:
化学工程
·
催化
·
可再生能源
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2022
·Vol. 46
·期 14
·6756-6764
·
IF 3.925
Boyong Ye,Wenyang Zhang,Ruru Zhou,Yuanyuan Jiang,Zixin Zhong,Zhaoyin Hou
The dehydration of fructose to 5-hydroxymethylfurfural (5-HMF) is a crucial step in the biorefinery process, and finding a recyclable solid-acid catalyst and green solvent remains a challenge. In this work, a mesoporous sulfonated high-crosslinked polymer (abbreviated as SHCP) was synthesized following a facile route and used in the dehydration of fructose to 5-HMF in different solvents. The structure and properties of SHCP were characterized using N2 adsorption–desorption, XRD, Raman, SEM, TEM, FTIR, 13C CP/MAS NMR and XPS techniques. It was confirmed that SHCP possesses high surface area, uniform mesoporous and abundant sulphonic groups, and it can promote the dehydration of fructose to 5-HMF under mild reaction conditions. At the same time, the performance of SHCP in different solvents was tested in detail, it was found that SHCP exhibited similar initial activity in 1,4-dioxane/H2O mixture as that in dimethyl sulfoxide (DMSO), while the stability of SHCP in 1,4-dioxane/H2O mixture was enhanced obviously compared with that in DMSO. The reason for the deactivation of SHCP in different solvents was discussed, and it was disclosed that a small amount of water in DIO could depress the oligomerization of 5-HMF and enhance the stability of SHCP.
研究领域:
化学工程
·
催化
·
绿色化学
·
生物精炼
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Haodong Chu,Xinqiang Feng,Xue Wu,Jianting Song,Chun Shen,Tianwei Tan
Green and efficient upgrading of cellulose into p-xylene (PX) is critical to utilizing zymotic biomass wastes and complies with the “recycling economy”. Despite the tremendous efforts devoted by researchers, a bio-based PX production route that is compact with both technical and economic feasibility is extremely desirable but still remains a significant challenge. Here, we put forward a brand new two-step PX production route via 2,5-hexanedione (HDO), efficiently simplifying the whole process and cutting down the cost. We thoroughly investigated the effect of reaction conditions and took insight into the corresponding reaction mechanism in each step. The highest yields of 64 and 85% were achieved for HDO/2,5-dimethylfuran (DMF) and PX during the first and second steps, respectively. Furan ring hydrogenation and condensation into an oligomer comprise the main side reactions during the first step. In comparison with the most promising production route for bio-based PX at present (cellulose → glucose → fructose → 5-hydroxymethyl furfural (HMF) → DMF → PX), the as-proposed two-step route may exhibit tremendous advantages: streamlining with much less operating units and laying solid foundation for industrialized production by dexterously avoiding production and separation of HMF.
研究领域:
化学工程
·
生化工程
·
可再生能源
·
可持续化学
✓ 已验证
产品关联
DOI
高影响因子
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.
研究领域:
生物化学
·
生物技术
·
酶工程
·
催化
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-12
·
IF 16.6
Zhou Hua,Ren Yue,Yao Bingxin,Li Zhenhua,Xu Ming,Ma Lina,Kong Xianggui,Zheng Lirong,Shao Mingfei,Duan Haohong
Electrooxidation of biomass platforms provides a sustainable route to produce valuable oxygenates, but the practical implementation is hampered by the severe carbon loss stemming from inherent instability of substrates and/or intermediates in alkaline electrolyte, especially under high concentration. Herein, based on the understanding of non-Faradaic degradation, we develop a single-pass continuous flow reactor (SPCFR) system with high ratio of electrode-area/electrolyte-volume, short duration time of substrates in the reactor, and separate feeding of substrate and alkaline solution, thus largely suppressing non-Faradaic degradation. By constructing a nine-stacked-modules SPCFR system, we achieve electrooxidation of glucose-to-formate and 5-hydroxymethylfurfural (HMF)-to-2,5-furandicarboxylic acid (FDCA) with high single-pass conversion efficiency (SPCE; 81.8% and 95.8%, respectively) and high selectivity (formate: 76.5%, FDCA: 96.9%) at high concentrations (formate: 562.8 mM, FDCA: 556.9 mM). Furthermore, we demonstrate continuous and kilogram-scale electrosynthesis of potassium diformate (0.7 kg) from wood and soybean oil, and FDCA (1.17 kg) from HMF. This work highlights the importance of understanding and suppressing non-Faradaic degradation, providing opportunities for scalable biomass upgrading using electrochemical technology.
研究领域:
化学工程
·
电化学
·
可持续化学
·
生物质转化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Biotechnology for Biofuels and Bioproducts
·
2023
·Vol. 16
·期 1
·1-13
·
IF 0
Yang Fan,Liu Jiashu,Li Bianxia,Li Huanan,Jiang Zhengbing
Background As a cost-effective and eco-friendly approach, biocatalysis has great potential for the transformation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA). However, the compatibility of each enzyme in the cascade reaction limits the transformation efficiency of HMF to FDCA. Results Coupled with an alcohol oxidase from Colletotrichum gloeosporioides ( Cgl AlcOx), this study aims to study the potential of bacterial laccase from Bacillus pumilus ( Bp Lac) in an enzymatic cascade for 2,5-furandicarboxylic acid (FDCA) biosynthesis from 5-hydroxymethylfurfural (HMF). Bp Lac showed 100% selectivity for HMF oxidation and generated 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). Cgl AlcOx was capable of oxidizing HMFCA to 2-formyl-5-furancarboxylic acid (FFCA). Both Bp Lac and Cgl AlcOx could oxidize FFCA to FDCA. At the 5 mM scale, a complete transformation of HMF with a 97.5% yield of FDCA was achieved by coupling Bp Lac with Cgl AlcOx in the cascade reaction. The FDCA productivity in the reaction was 5.3 mg/L/h. Notably, Bp Lac could alleviate the inhibitory effect of FFCA on Cgl AlcOx activity and boost the transformation efficiency of HMF to FDCA. Moreover, the reaction was scaled up to 40 times the volume, and FDCA titer reached 2.6 mM with a yield of 58.77% at 168 h. Conclusions This work provides a candidate and novel insight for better design of an enzymatic cascade in FDCA production.
研究领域:
生物催化
·
生物化学
·
化学工程
·
酶学
✓ 已验证
产品关联
DOI
PubMed
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Xuemin Zhong,Peng Yuan,Yanfu Wei,Dong Liu,Dusan Losic,Mengyuan Li
The aerobic oxidation of 5-hydroxymethylfurfural (HMF), a key platform compound derived from biomass, to 2,5-furandicarboxylic acid (FDCA) is a highly important reaction in the production of green and sustainable chemicals. Here, we developed a highly efficient and stable halloysite-supported Pt–Au alloy catalyst for the selective oxidation of HMF to FDCA. The catalyst was synthesized through the organosilane functionalization of halloysite nanotubes, followed by the in situ formation and dispersion of Pt–Au alloy nanoparticles on the internal and external surfaces of nanotubes. The composition, morphology, and structure of the prepared catalyst were characterized. The catalyst with the optimal composition of Pt/Au molar ratio of 1/4 and metal loading of 1.5 wt % exhibited outstanding catalytic activity for the oxidation of HMF to FDCA using O2 as an oxidant with 100% conversion of HMF and 99% selectivity of FDCA. This excellent catalytic performance is mainly attributed to the high dispersion and alloying effects of bimetallic nanoparticles, which promoted the activation of reactants or intermediates and further improved FDCA selectivity. Furthermore, the halloysite-supported Pt/Au bimetallic catalyst showed high stability and reusability. This study provides a promising strategy by combining clay mineral halloysite and bimetallic alloys for developing efficient catalysts with high FDCA selectivity and stability for the oxidation of HMF to FDCA.
研究领域:
催化
·
纳米材料
·
绿色化学
·
可持续化学
✓ 已验证
DOI
PubMed
高影响因子
ChemCatChem
·
2020
·Vol. 12
·期 12
·3257-3264
·
IF 4.853
Xue-Ying Zhang,Xin Wang,Nan-Wei Li,Ze-Wang Guo,Min-Hua Zong,Ning Li
Graphical Whole-cell biocatalysis : Cofactor-engineered E. coli cells proved to be versatile catalysts to produce furan carboxylic acids from toxic biobased furans with high productivities. The introduction of NADH oxidase (NOX) into E. coli harboring aldehyde dehydrogenases (ALDHs) significantly promoted intracellular NAD + regeneration, thus enhancing ALDH-catalyzed aldehyde oxidation. A group of aromatic aldehydes was efficiently oxidized to target carboxylic acids. More importantly, these engineered whole-cell biocatalysts displayed high substrate tolerance toward toxic furans. Furan carboxylic acids are useful chemicals in various industries. In this work, biocatalytic production of furan carboxylic acids was reported with high productivities by cofactor-engineered Escherichia coli cells. NADH oxidase (NOX) was introduced into E. coli harboring aldehyde dehydrogenases (ALDHs) to promote intracellular NAD + regeneration, thus significantly enhancing ALDH-catalyzed oxidation. These engineered biocatalysts were capable of efficient aerobic oxidation of a variety of aromatic aldehydes. More importantly, they exhibited high substrate tolerance toward toxic furans. E. coli co-expressing vanillin dehydrogenase and NOX ( E. coli_ CtVDH1_NOX) enabled efficient oxidation of 250 mM of 5-hydroxymethylfurfural (HMF) to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), providing a productivity of 3.7 g/L h. With E. coli_ CtVDH2_NOX as catalyst, up to 240 mM of furfural and 5-methoxymethylfurfural (MMF) could be smoothly oxidized. 2-Furoic acid (FCA, 227 mM) and 5-methoxymethyl-2-furancarboxylic acid (MMFCA, 287 mM) were produced in fed-batch synthesis, providing the productivities of 2.0 and 5.6 g/L h, respectively.
研究领域:
生物技术
·
生物化学工程
·
代谢工程
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL DAIRY JOURNAL
·
2023
·
IF 3.1
Hongbo Li,Meng Bian,Yuelu Jiang,Chunshuang Li,Yang Zou,Xiaohong Chen,Hongjuan Li,Jinghua Yu
To better monitor and reduce the generation of Maillard reaction products (MRPs) during the heat treatment and storage of dairy products , a reaction kinetic model was established to evaluate the inhibitory effects of tea polyphenols on MRPs in the milk simulation system. The inhibition of MRPs by tea polyphenols followed first order kinetics, while the inhibition of 5-hydroxymethyl-2-furfural (5-HMF) was most pronounced at 95 °C with the reaction rate constant of −0.0683 d −1 . Arrhenius model showed that the conversion rate of 5-HMF (35.672 d −1 ) was higher than N ε -carboxyethyllysine (2.585 d −1 ) and N ε -carboxymethyllysine (0.53 d −1 ) after the addition of tea polyphenols, which indicated that 5-HMF was the main intermediate product of Maillard reaction. Moreover, the shelf life of the two-stage sterilised milk containing tea polyphenols was 141 d, which was 2.1 times longer than that of the control sample (67 d), which provided reference for consumers during the drinking period.
研究领域:
食品科学
·
化学动力学
·
乳品技术
·
食品保鲜
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2023
·
IF 6
Zhongyuan Sun,Yujiao Xie,Chunjie Wei,Feipeng Wang,Yuan Zhang,Feng Song,Hongyou Cui
Metal chloride aqueous solution is an effective method to promote the conversion of cellulose into 5-hydroxymethylfurfural (HMF). In this work, the influences of sodium chloride (NaCl) and lithium chloride (LiCl) on the conversion of cellulose into HMF in ferric chloride (FeCl 3 ) aqueous solution were investigated. The conversion of glucose and fructose in FeCl 3 –NaCl and FeCl 3 –LiCl aqueous solutions were studied, and the interaction between active species and cellobiose was characterized by UV spectrum and electrospray ion mass spectrometry to explore salt addition on the reaction of cellulose conversion and the active specie. Results showed that the yield of HMF converted from cellulose in FeCl 3 aqueous solution was low, while the yield of HMF was significantly increased when NaCl or LiCl added to the system. In FeCl 3 –NaCl aqueous solutions, the yield of HMF reach a maximum of 40.0% at a concentration of 0.02 M FeCl 3 , and hydrolysis of cellulose was the key step in the conversion of cellulose; In FeCl 3 –LiCl aqueous solutions, the yield of HMF reach a maximum of 36.7% at a concentration of 0.06 M FeCl 3 , and isomerization of glucose was the controlling step. The characterization results illustrated that the addition of NaCl or LiCl changed the active species in FeCl 3 aqueous solutions, and [Fe(OH) 2 ] + and [FeCl 2 (OH) + Li] + were the active species in FeCl 3 –NaCl and FeCl 3 –LiCl aqueous solution for cellulose conversion, respectively.
研究领域:
化学工程
·
材料科学
·
分析化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Rong Shang,Hao Zhang,Yulong Li,Bang Gu,Qinghu Tang,Feng Qiu,Qiu-E Cao,Wenhao Fang
The synthesis of primary amines from renewable biobased carbonyl compounds via reductive amination has received much attention. Modifying the surface structure of a heterogeneous catalyst may offer prospects to address selectivity maneuvering in this complex amination process. In this work, a metal–organic framework (MOF)-derived carbon-coated strategy was adopted to prepare the Ni@C catalysts with different thicknesses of carbon shells. This type of Ni catalyst achieved 98% yield of (5-(aminomethyl)furan-2-yl)methanol (AMF) at 100 °C under 2 bar of H2 from reductive amination of 5-hydroxymethylfurfural (HMF, an important cellulose-derived platform molecule) with NH3·H2O. In comparison, a Ni-NiO catalyst obtained by reducing NiO with H2 would mainly overhydrogenate AMF to (5-(aminomethyl)tetrahydrofuran-2-yl)methanol (THAMF, 52% in yield) as a byproduct. The modification of the electronic structure of Ni0 active sites with a carbon shell was elucidated, demonstrating electron-rich Ni0 sites for H2 activation. Moreover, different HMF adsorption modes on Ni-NiO and Ni@C surfaces were illustrated, significantly affecting the product distribution. Subsequently, distinctive NH3·H2O activation processes were proposed for both Ni catalysts to understand selective conversion of the Schiff base (i.e., the critical reaction intermediate). The developed Ni@C catalyst with suitable carbon thickness, abundant Ni0 centers, and defective carbon species showed high AMF yield under mild reaction conditions, facile separation–regeneration, and satisfying reusability. In addition, this Ni catalyst can also provide a relatively good substrate scope toward bioamine synthesis via reductive amination.
研究领域:
催化
·
有机化学
·
材料科学
·
绿色化学
·
化学工程
·
可再生能源
·
表面化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）