Journal of Energy Chemistry
·
2022
·
IF 13.599
Yanwei Zhu,Jianqiao Shi,Yingying Li,Yuxuan Lu,Bo Zhou,Shuangyin Wang,Yuqin Zou
Surface segregation is ubiquitous in multi-component materials and is of great important for catalysis but little is known on the surface structure under graphene encapsulation. Here, we show that the graphene encapsulated CoCu performs well for the electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) with the onset potential before 1.23 V RHE and a nearly 100% selectivity of FDCA under 1.4 V RHE . From the experimental results, the unprecedented catalytic performance was attributed to local structural distortion and sub-nanometer lattice composition of the CoCu surface. We accurately show the dispersed Cu doped Co 3 O 4 nano-islands with a lot of edge sites on the bimetallic Co-Cu surface. While, the gradient components effectively facilitate the establishment of built-in electric field and accelerate the charge transfer. Theoretical and experimental results reveal that the surface Co and neighbouring Cu atoms in sub-nanometer lattice synergistically promote the catalysis of HMF. This work offers new insights into surface segregation in tuning the element spatial distribution for catalysis.
研究领域:
材料科学
·
电化学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2023
·Vol. 13
·期 6
·969
·
IF 3.9
Srinivasan Vinju Vasudevan,Jin Cai,Junming Xu,Hongjian Lin,Hongliang Wang,Quan Bu
In this work, the microwave-assisted reaction of 5-hydroxymethylfurfural (5-HMF) into valuable ether and acylated production formation was investigated with the help of molybdophosphoric acid encapsulated dendritic fibrous silica (KCC-1) as a catalyst. XRD, N2adsorption-desorption, SEM, FT-IR, NH3-TPD, and TEM were used to analyze the physicochemical and structural properties of the synthesized catalysts. The microwave etherification of 5-HMF with ethanol was tested using synthesized catalysts. The effects of the reaction temperature, reaction time, catalytic amount, and microwave power were investigated. The resulting MPA-KCC-1 and IMPA-KCC-1 catalysts demonstrated excellent activity for the etherification of 5-HMF with ethanol, producing 5-(hydroxymethyl) furfural diethyl acetal (HMFDEA) and 5-(ethoxymethyl)furfural diethyl acetal (EMFDEA) products selectively. The significant advantages of the work are the selective production of EMFDEA at 82%, the catalyst can be easily removed via filtration, and the catalyst activity remains nearly intact even after five reaction cycles.Keywords:biomass;acetylation;5-HMF;etherification;heteropolyacid;fibrous silica
研究领域:
化学工程
·
催化材料
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Xiangyu Jia,Kai Yuan,Guofu Wang,Shanhui Zhu,Mei Dong,Jiamin Wang,Xiaoming Li,Weibin Fan
Selective reduction of 5-hydroxymethylfurfural (HMF) to valuable 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) remains a significant challenge under mild conditions. The synergistic effect between metal single atoms (SAs) and nanoparticles (NPs) can greatly enhance catalytic activity. Here, a high-performance Pd SAs catalyst supported on N-doped carbon (PdSAs/NC) was developed from Pd@UiO-66-NH 2 . It was found that partial Pd SAs were spontaneously restructured into Pd NPs during the reaction. Our catalyst exhibited 100 % conversion of HMF and 98 % selectivity towards BHMTHF at temperature as low as 0 °C. In situ FTIR spectra results and density functional theory calculations indicate that Pd SAs contribute to the C = O activation, while Pd NPs facilitated the H 2 dissociation into H* atoms, resulting in synergistic catalytic activity between Pd SAs and Pd NPs.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2017
·Vol. 19
·期 21
·5103-5113
·
IF 9.125
Ying Duan,Min Zheng,Dongmi Li,Dongsheng Deng,Lu-Fang Ma,Yanliang Yang
The catalytic conversion of HMF to 2-hydroxy-3-methyl-2-cyclopenten-1-one (MCP), which is a valuable edible essence that has traditionally been obtained from adipic acid, was achieved with an isolated yield of 58%. This procedure comprised two steps: the hydrogenation of 5-hydroxymethylfurfural (HMF) to 1-hydroxy-2,5-hexanedione (HHD) in water on Pd/Nb2O5 catalysts and then the isomerization of HHD to MCP in the presence of a base. The Nb2O5 supports, which were acidic, were characterized by FTIR, XRD and NH3-TPD. The supported Pd/Nb2O5 catalysts, in which Pd was highly dispersed, were synthesized employing cyclohexene as a reductant and were characterized by XRD, TEM, ICP-AES, XPS, EDX and CO pulse chemisorption. The high conversion of HMF was attributed to the high dispersion of Pd, and the acidity of the supports led to high selectivity for HHD. The conversion of HHD to MCP was an intramolecular aldol condensation reaction, and the protonic solvent favored this reaction. Ca–Al was proved to be an effective solid base for the conversion of HHD to MCP in water.
研究领域:
化学工程
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS LETTERS
·
2023
·
IF 2.8
Xu Lingling,Pan Xiaomei,Wu Ningxin,Gao Lijing,Xiao Guomin
The conversion of biomass energy sources is a crucial direction in the transformation of energy resources, such as cellulose to high-value chemicals. As an important platform compound, 5-hydroxymethylfurfural (HMF) is one of the worthwhile products from biomass. Previously, the use of Hf/ZSM-5 catalyst demonstrated excellent catalytic performance, with the yield of HMF reaching 67.50% under optimal reaction conditions (120 min, 190 °C, H 2 O(NaCl)/THF). Based on the previous work, the effect of a series of metal salts on the preparation of HMF from cellulose catalyzed by Hf/ZSM-5 catalyst was investigated in this paper. This result demonstrates the addition of AlCl 3 promoted the production of HMF yield and AlCl 3 completed with excellent performance among five metal salts. Moreover, the yield of HMF was improved to 70.95% by adjusting the optimal reaction conditions. Graphical Abstract
研究领域:
化学工程
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS LETTERS
·
2020
·Vol. 151
·期 7
·1984-1992
·
IF 2.482
Wu Ningxin,Zhang Manling,Pan Xiaomei,Zhang Jin,Gao Lijing,Xiao Guomin
Abstract The production of 5-hydroxymethylfurfural (HMF) from cellulose is of great significance for the high-value utilization of biomass, although this route currently faces the challenge of low efficiency. In the present work, a series of effective (x)Hf/ZSM-5 catalysts were developed for HMF production from cellulose, and analyzed by BET, XRD, SEM, ICP, NH 3 -TPD, Py-FTIR techniques. Driven by the (5)Hf/ZSM-5 catalyst, HMF with a yield of up to 67.5% and 17.2% of furfural are simultaneously obtained from cellulose in the H 2 O (NaCl) /THF biphasic system. Moreover, after four consecutive cycles, (5)Hf/ZSM-5 catalyst still maintained part of its catalytic activity. The 67.5% HMF yield achieved herein is one of the highest yields achieved in the conversion reaction using cellulose as a substrate, and the catalytic performance of the H 2 O (NaCl) /THF system containing the (5)Hf/ZSM-5 catalyst is even comparable to that of the expensive ionic liquid system. This result reflects the application prospect of (5)Hf/ZSM-5 catalyst in the future industrial production process of HMF. Graphic Abstract
研究领域:
化学工程
·
催化
·
生物质转化
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Mufan Wang,Shiying Fan,Xinyong Li,Jugong Shi,Yan Mao,Yaqi Yang,Gao Li
Efficiently upgrading 5-hydroxymethylfurfural (HMF) into high-value-added products, such as 2,5-diformylfuran (DFF) and 2,5-furan dicarboxylic acid (FDCA), through a photocatalytic process by using solar energy has been incessantly pursued worldwide. Herein, a series of transition-metal (TM = Ni, Fe, Co, Cu) single atoms were supported on Ti4+αTi3+1-αO2−δ nanofibers (NFs) with certain defects (Ov), denoted as TM SAC-Ti4+αTi3+1-αO2−δ NFs (TM = Ni, Fe, Co, Cu), aiming to enhance the photocatalytic conversion of HMF. A super HMF conversion rate of 57% and a total yield of 1718.66 μmol g–1 h–1 (DFF and FDCA) surpassing that of the Ti4+αTi3+1-αO2−δ NFs by 1.6 and 2.1 times, respectively, are realized when TM is Co (Co SAC-Ti4+αTi3+1-αO2−δ NFs). Experiments combined with density functional theory calculation (DFT) demonstrate that the TM single atoms occupy the Ti site of Ti4+αTi3+1-αO2−δ NFs, which plays a dominant role in the photo-oxidation of HMF. Raman, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) characterizations confirm the strong electron local exchange interaction in TM SAC-Ti4+αTi3+1-αO2−δ NFs and demonstrate the substitution of Ti by the TM SACs. The projected density of states and charge density difference reveal that the strong interaction between metal-3d and O-2p orbitals forms Ti–O–TM bonds. The bonds are identified as the adsorption site, where TM single atoms on the surface of Ti4+αTi3+1-αO2−δ NFs reduce HMF molecule adsorption energy (Eads). Furthermore, the TM single atom modulates the electronic structure of TM SAC-Ti4+αTi3+1-αO2−δ NFs through electron transfer, leading to narrow band gaps of the photocatalysts and enhancing their photocatalytic performance. This study has uncovered a newer strategy for enhancing the photocatalytic attributes of semiconducting materials.
研究领域:
材料科学
·
化学工程
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2024
·
IF 2.2
Peng Wang,Jun-Fei Gu,Zhan Chen,Hao-Yue Ma,Xing-Chuan Li,Shuai Li,Xiang-Ya Xu,Ye Yuan,Cheng Chen,Zongkui Kou
Graphical This study develops a solid-state thermal (SST) synthesis method for the one-step preparation of MOF-derived Mn x @NC catalysts. Among these, the optimal catalyst (Mn 2.5 @NC) exhibits excellent activity, remarkable stability, and good recyclability for HMF oxidation to FDCA, achieving an FDCA yield of 94 % within 4 h at room temperature and maintaining its catalytic performance for five cycles without activity decay. Transforming the bio-based 5-hydroxymethylfurfural (HMF) into its oxidation product 2,5-furandicarboxylic acid (FDCA) offers an attractive route for synthesizing bioplastic monomers. However, significant challenges remain in developing efficient and stable non-precious metal catalysts. Here, we employed a solid-state thermal synthesis (SST) method to design and synthesize a series of metal-organic framework (MOF)-derived metal-nitrogen-carbon (M@NC) materials with gradient metal contents and low metal loadings, labeled as Mn x @NC, for converting HMF into FDCA through oxidation. Further investigations revealed that the amount of metal doping significantly influenced the catalyst structure, particularly in terms of defect quantity and specific surface area. The optimal catalyst, Mn 2.5 @NC, exhibited the largest specific surface area and the highest number of defects, achieving a 94 % FDCA yield within 4 h. Experimental results demonstrated that the recovered catalyst could be reintroduced into the reaction system and maintained selectivity comparable to that of the fresh catalyst for at least five cycles. Moreover, various characterizations of both fresh and recovered catalysts confirmed the great stability of Mn 2.5 @NC. This study provides advanced insights into the effective catalytic conversion of HMF to FDCA and highlights the importance of structural design and regulation in optimizing M@NC catalysts.
研究领域:
化学工程
·
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2021
·
IF 6.165
Ting Huang,Huang-xian Zhang,Xiao-hua Zhang,Da-yong Peng,Xu-liang Nie,Jing Chen,Wan-ming Xiong
A kind of functionalized diallylimidazole ionic liquids (CnDAIMF) was synthesized and applied in the dehydration of D-fructose to produce 5-HMF under the microwave radiation. The results showed that X-ray, 1 H NMR and FT-IR confirmed the production. The target ILs existed in a highly centrally symmetric, and crystalline state at room temperature, with a good thermal stability up to 300 °C (HTD ≥ 340 °C). In the experiments of conversion D-fructose to 5-HMF, 5-HMF could be obtained via the catalysis of diallylimidazole IL whether in water or DMSO. The catalytic performance of these ILs was not much different from that of solid acid (like camphor sulfonic acid or solid carbon sulfonic acid), and which was higher than that of the monoimidazole hexafluorophosphate or imidazole class bromine salt, but there were no obvious changes can be found with the variation of carbon chain length between imidazole rings in diallylimidazole IL. The effects of temperature and solvent on the reaction were more significant. The optimized yield of 5-HMF was 52.59% at 185 °C in a water-C 2 DAIMF solvent (t = 10 min), while 73.71% at 195 °C in DMSO-C 2 DAIMF solvent. Furthermore, six CnDAIMF have a considerable effect on the conversion in water and 5-HMF yield of about 50% could be obtained, which is satisfactory compared with other similar processes, especially in the microwave system of aqueous solution. Therefore, this process may be benefit for many researches and applications related to functionalized ionic liquid research and biomass conversion applications.
研究领域:
化学工程
·
生物质能
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2025
·
IF 6.5
Gui-Rong Zhang,Zhiyuan Sun,Xinyu Liu,Jiansong Wang,He Li,Xiaoliang Qu,Hui Yu,Liu-Liu Shen,Donghai Mei
Electrooxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a promising strategy for biomass valorization. However, a significant challenge arises from the substantial carbon loss due to spontaneous HMF degradation in alkaline electrolytes, particularly at high concentrations. In this study, we present a straightforward approach to mitigating carbon loss during the electrochemical conversion of HMF to FDCA by suppressing non-Faradaic degradation through low-temperature electrolysis. Notably, under conventional room temperature conditions, carbon losses of up to 25 % can occur, whereas our low-temperature electrolysis method reduces carbon loss to negligible levels (< 1 %) even at high HMF concentrations (up to 500 mM) in highly alkaline electrolyte (2.0 M KOH). This strategy effectively addresses the long-standing challenge of balancing the enhanced kinetics of HMF electrooxidation with the accelerated degradation of HMF as its concentration increases in alkaline media. Our findings highlight the critical role of suppressing non-Faradaic degradation in the efficient conversion of HMF and demonstrate that low-temperature electrolysis offers a viable solution to the challenges of industrial-scale electrochemical biomass valorization.
研究领域:
化学工程
·
能源化工
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS COMMUNICATIONS
·
2019
·
IF 3.674
Tingwei Zhang,Wenzhi Li,Haosheng Xin,Lele Jin,Qiying Liu
An Al 3+ -modified formaldehyde-p-hydroxybenzenesulfonic acid resin catalyst (Al-SPFR) was synthesized through a hydrothermal method. N 2 adsorption–desorption experiment and acid–base titration revealed that the Al-SPFR catalyst had better texture properties and higher strong acid content than the previously prepared unmodified SPFR . The effects of reaction time and temperature, catalyst loading, and water content in water/GVL mixture were investigated for glucose dehydration using Al-SPFR as the catalyst. An HMF yield of 47.4% was obtained at 170 °C for 2 h in the biphasic GVL/H 2 O medium. Further performing a five-cycle experiment, the HMF yield initially decreased and then remained fairly constant, and the recyclability of the Al-SPFR was reasonable.
研究领域:
化学工程
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2024
·
IF 5.2
Yang Gao,Shilin Fan,Bin Zhu,Soliman I. El-Hout,Jinghui Lyu,Jian Zhang,Chunlin Chen
Biomass energy has gained significant attention due to its renewability and clean, low-carbon characteristics. We prepared a Co@NC-a catalyst using the complexation-carbonation-acid etching method, which can catalyze both thermochemical and electrochemical HMF selective oxidation reactions. In thermocatalysis, it can achieve 100 % HMF conversion and 94.4 % FDCA yield at 65 °C and 0.2 MPa O 2 . In electrocatalysis , 100 % HMF conversion and 73 % FDCA yield were also realized. Significantly, graphitized carbon contributes to the aerobic oxidation of HMF due to its excellent electrical conductivity , which promotes electron transfer during the reaction. Additionally, a comparative study of the activation energy of this catalytic system in electrocatalysis and thermocatalysis showed that electrocatalysis is kinetically more favorable. The energy efficiency calculation also indicates electrocatalysis is more energy efficient than thermocatalysis.
研究领域:
生物质能
·
催化化学
·
材料科学
✓ 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）