CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Canyan Yang,Ruichen Wang,Chao Yu,Jinhua Xiao,Zhiwei Huang,Bihong Lv,Huawang Zhao,Xiaomin Wu,Guohua Jing
Cu-based catalysts inevitably undergo surface reconstruction during the electrochemical carbon dioxide reduction reaction (CO 2 RR) process. Thus, it is a challenge to construct stable Cu + -Cu 0 sites of Cu-based catalysts. In this study, we report a simple and facile engineering strategy for stable Cu + -Cu 0 sites and oxygen defects derived from the boron-doped copper composite catalyst (B-Cu x O) as an efficient CO 2 RR electrocatalyst. The 5 % B-Cu x O exhibited 48.44 % C 2+ products Faraday efficiency (FE) for 12 h at −1.0 V vs reversible hydrogen electrode (RHE) in H-cell, which was far superior to Cu x O (23.85 %). Combining density functional theory (DFT) and in situ Attenuated Total Reflection Fourier Transform Infrared spectroscopy ( in situ ATR-FTIR), a higher electronic depletion on the catalyst surface inhibited the electrons accumulation around Cu sites, thereby maintaining the positive charge and inhibiting the complete reduction of Cu + . Moreover, the high oxygen defects in 5 % B-Cu x O could effectively activate CO 2 into *CO. We emphasized that Cu + functioned as the primary active site by facilitating adsorption and dimerization of *CO, whereas Cu 0 assisted in optimizing CO 2 activation.
研究领域:
材料科学
·
电化学
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高影响因子
ChemSusChem
·
2026
·Vol. 19
·期 3
·e202502450
·
IF 5.9
Mengmeng Jin,Yaolei Zhao,Weiting Li,Tiantian Xu,Jiazuo Wei,Jingjun Liu
2,5-Bis(hydroxymethyl)furan (BHMF) is a promising intermediate for the synthesis of pharmaceuticals and crown ethers, whereas achieving a high reaction rate in the hydrogenation of 5-hydroxymethylfurfural (5-HMF) to form BHMF remains challenge. In this work, a series of Cu/CeO 2 –x catalysts ( x denotes H, Air, Ar) were synthesized by calcination under different atmospheres (10% H 2 /Ar, Air, Ar) and evaluated for the 5-HMF hydrogenation to BHMF. Cu/CeO 2 –Ar exhibited a superior reaction rate of 26.8 mmol·g cat −1 ·h −1 and BHMF yield of 99.1% under the condition (180°C, 5 h, 1 MPa H 2 ), significantly outperforming Cu/CeO 2 –H and Cu/CeO 2 –Air. The characterizations reveal that the calcination in the oxygen-deficient argon atmosphere led to high Cu dispersion and minimized Cu particle size in the Cu/CeO 2 –Ar. These properties resulted in the abundant Cu + –O V –Ce 3+ sites and increased Cu 0 number. In situ Fourier transform infrared spectroscopy analysis elucidates the distinct roles of these active sites. Cu + sites are responsible for perpendicular adsorption of the 5-HMF carbonyl group, and Cu 0 sites drive efficient H 2 dissociation. In contrast, the O V –Ce 3+ sites do not adsorb 5-HMF and H 2 . The close synergy between numerous Cu 0 sites and abundant Cu + sites in the Cu/CeO 2 –Ar accelerates the process of 5-HMF hydrogenation to BHMF. Graphical The oxygen-deficient argon atmosphere led to high dispersion and small particle size of Cu in Cu/CeO 2 –Ar. These properties resulted in the abundant Cu + sites for the adsorption of CO from 5-HMF and the numerous Cu 0 sites to efficiently dissociate H 2 , synergistically boosting catalytic reaction rate to 26.8 mmol·g cat -1 ·h -1 .
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PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Xueyang Jing,Dehe Fan,Yumeng Li,Ruopeng Li,Maozhong An,Peixia Yang,Jinqiu Zhang
Electrochemical CO 2 reduction reaction (CO 2 RR) coupled with renewable electricity offers a promising strategy to convert CO 2 into value-added chemicals while addressing the challenges of carbon emissions. Although copper-based catalysts have demonstrated promising capability in CO 2 -to-hydrocarbon conversion, achieving highly selective and energy-efficient production of C 2+ products, particularly ethylene (C 2 H 4 ), remains a significant challenge. Herein, we report a novel strategy to construct oxidation-derived copper (ODCu) nanowire catalysts through a combination of electrodeposition, wet-chemical synthesis, and cyclic voltammetry (CV) redox process. During the CV treatment, the catalyst undergoes in situ surface reconstruction, resulting in the formation of abundant Cu + /Cu 0 interfaces. The optimized ODCu nanowire catalyst exhibits remarkable C 2 H 4 selectivity with a faradaic efficiency (FE) of 54 % ± 4 % and a partial current density of 154 ± 12 mA·cm −2 at −1.0 V (vs reversible hydrogen electrode, RHE), demonstrating stable performance for 12 h. Through in situ infrared spectroscopy (FTIR) analysis and density functional theory (DFT) calculations, we reveal that the engineered Cu + /Cu 0 interfaces significantly lower the activation energy barrier for C C coupling, thereby promoting the selective formation of C 2 H 4 . This work provides new insights into interface engineering for enhanced CO 2 RR performance and offers an effective strategy for developing high-performance copper-based electrocatalysts.
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PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2026
·
IF 6.9
Xiaofang Wen,Hongcan Lou,Zheng Li,Jiehao Xie,Zirui Qin,Xingkun Chen,Yuan Tan,Nian Lei,Wei Lu,Yunjie Ding
The development of efficient catalysts for the selective hydrogenation of dimethyl oxalate (DMO) to high-value oxygenates is of great industrial importance. This study presents a systematic investigation into the promotional effect of gallium (Ga) on Cu/SiO 2 catalysts for tailoring product selectivity in DMO hydrogenation. A series of Ga x Cu 30 /SiO 2 catalysts with varying Ga loadings (x = 0.5, 1, 3 wt%) were synthesized via the ammonia evaporation method. With a moderate Ga doping of 0.5 wt%, the Ga 0.5 Cu 30 /SiO 2 catalyst achieved an exceptional ethylene glycol (EG) yield of 74 %, which is three times higher than its Ga-free counterpart (23 %). Further increases in Ga loading to 1 and 3 wt% redirected the reaction pathway, steering the selectivity towards ethanol (ET, 81 %) and 2-methoxyethanol (MT, 54 %), respectively. Characterization by N 2 O titration, XRD, XPS, in situ FT-IR and H 2 -TPR revealed that Ga incorporation fine-tunes the synergy between metallic Cu 0 (for H 2 dissociation) and Cu + sites (for C=O bond polarization). Concurrently, the generated surface acid sites facilitate subsequent dehydration and hydrogenolysis steps. Consequently, the catalytic performance is directly correlated with the evolution of Cu valence states and surface acidity. This work provides a rational strategy for designing multifunctional catalysts for the selective synthesis of target chemicals from DMO.
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高影响因子
ChemCatChem
·
2021
·Vol. 13
·期 19
·4164-4181
·
IF 5.686
Qiuli Fu,Shibo Yang,Ping Ning,Rongrong Miao,Liang He,Qingqing Guan
Graphical Selective hydrogenation : In rubber seed shell porous biochar supported Cu−Ni bimetals, the formed Cu 1 Ni 3 alloy stabilized the excessive Cu species which were in the lattice on the inner/outer surfaces of the rss AC support. The catalytic activity is retained, ensuring that the catalyst would neither be oxidized nor aggregated severely. The prepared high-efficiency Cu 1 Ni 1 / rss AC catalyst catalyzed the hydrogenation reaction of FAL to produce FOL, THFA and 2-MF. Using cheap Cu-based catalysts for highly selective hydrogenation of furfural (FAL) is of great importance of upgrading this biomass-derived platform molecule but is still challenging for large-scale application due to the low conversion efficiency and the easy aggregation of Cu active sites. To address these issues, a nitrogen-autodoped porous biochar derived from rubber seed shell ( rss AC) was fabricated for anchoring Cu sites on a nanoscale. Moreover, by the co-crystallization strategy of Cu and the second metal (M, M=Ni, Zn, Co, Ce), stable Cu−M nanoalloys were constructed on the surface of the rss AC support. The FAL hydrogenation experiments showed that the type, proportion and loading amount of the second metal had great effect on the catalytic efficiency. Compared with the other metals, Ni-doped Cu/ rss AC catalyst exhibited the best hydrogenation performance due to their extraordinary adsorption and activation capacity for hydrogen. Further, the highest catalytic efficiency was observed using 20 % Cu 1 Ni 1 /rss AC catalyst. The characterization results showed that the key to its success was highly-dispersive anchoring of the CuNi active sites onto the inner/outer surface of the nanopores of rss AC support by the strong interaction between the surface N-containing functional groups and metals. Of note, the formed CuNi alloys with the Cu/Ni atomic ratio of 1 : 3 played an important role in the stabilization of the adjacent nano-dot matrix Cu 0 species. Kinetic test indicated that the formation step of furfuryl alcohol (FOL) from FAL was still the key step and the hydrogenation products can be converted between FOL and tetrahydrofurfuryl alcohol (THFA). The life evaluation test showed that the catalyst still kept high activity and selectivity after being reused five times. The advanced synthesis method co-using N-doped support anchoring and the second metal alloying strategy sheds light on preparing effective catalysts for hydrogenation of biomass-based compounds.
研究领域:
化学工程
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材料科学
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催化反应
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DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Shangpu Zhuang,Yilin Lei,Fan Xue,Tao Wei,Jiahui Chu,Mifen Cui,Zhuxiu Zhang,Ruiping Wei,Jihai Tang,Xu Qiao
Unraveling the synergistic interplay between Cu 0 /Cu + and support sites in Cu-based catalysts, coupled with oxygen vacancy-mediated active site modulation and their impact on hydrogenation performance metrics, remains a critical challenge in heterogeneous catalysis. Herein, we engineered a family of MOF-derived Cu/CeO 2 catalysts with tunable Cu loadings and oxygen vacancy(O V ) concentrations, featuring Cu 0 -Cu + -O V interfacial sites, through a MOF-mediated pyrolysis strategy. Operando DRIFTS, XPS, and Raman analyses revealed dynamic restructuring of active sites during hydrogenation of cyclohexyl acetate. The optimized catalyst achieved 98.0 % substrate conversion and 97.3 % cyclohexanol selectivity at 250 ℃ under 3 MPa H 2 , exhibiting a TOF 2.8-fold higher than conventional Cu/CeO 2 . The results indicate that the superior catalytic performance of Cu/CeO 2 -MOF should be attributed to the synergistic effects of Cu + , Cu 0 , and O V . This synergy enhances the ability of catalysts to adsorb and activate cyclohexanone, as well as its hydrogen dissociation capability. Further analysis indicates that O V exerts a direct influence on product selectivity. Moreover, the concentration of O V modulates the ratio of Cu + /(Cu + +Cu 0 ), which significantly affects conversion efficiency of the reaction. This work introduces an innovative approach to designing the electronic structure of copper-based catalysts, thereby optimizing the hydrogenation reactions of carbonyl compounds.
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高影响因子
Catalysis Science & Technology
·
2022
·Vol. 12
·期 19
·5879-5890
·
IF 6.177
Dengfeng Dai,Chao Feng,Minmin Wang,Qingzhou Du,Dandan Liu,Yuan Pan,Yunqi Liu
Biomass-based chemicals as a renewable alternative to petroleum-based chemicals are of great significance. The conversion of biomass-based furfuryl alcohol to pentanediol, including 1,5-pentanediol and 1,2-pentanediol, is explored over a series of bifunctional Cu/MFI catalysts in a continuous-flow reactor. These catalysts are synthesized by supporting copper nanoparticles on MFI zeolites with varying molar ratios of SiO2/Al2O3. Among them, the Z60-10Cu catalyst containing balanced Cu0–Cu+ and Brønsted acid sites exhibits excellent performance, and a high furfuryl alcohol conversion of 99.5% and selectivity of 85.2% for 1,5-pentanediol (69.2%) and 1,2-pentanediol (16.0%) could be achieved (hydrogen pressure: 2.5 MPa) at 160 °C. The experimental results and the results obtained using the DFT technique revealed that the high catalytic activity realized during the processes of ring-opening and hydrogenation could be attributed to the synergistic effect between the Cu species and Brønsted acid sites. The Brønsted acid sites on the Si(OH)Al groups significantly affect the ring-opening process of furfuryl alcohol. The methoxy group on furfuryl alcohol adsorbs on the Cu+ sites, and the hydrogenation saturation of the ring-opening intermediate is realized under the influence of the activated hydrogen units on the Cu0 sites. The results reported herein could help promote the continuous production of high value-added pentanediol from biomass-based raw materials in the presence of non-noble metal catalysts. An economical and feasible path for the transformation of biomass resources into high value-added fine chemicals could also be developed.
研究领域:
生物化学
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催化化学
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材料科学
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高影响因子
FUEL
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2023
·
IF 7.4
Yuting Jin,Yanhong Quan,Yan Li,Jinxian Zhao,Jun Ren
A series of chainlike ZSM-5 supported Cu catalysts with the addition of citric acid (CA) was conveniently prepared using a complexation-impregnation method and employed in the methanol dehydrogenation to methyl formate (MF). The catalytic performance of Cu x /CZ5 first increased and then decreased with increasing CA/Cu ratio, reached 35.0% methanol conversion and 88.3% MF selectivity for Cu1.8/CZ5, significantly higher than that of Cu/CZ5. The superior catalytic performance might be principally explained by the higher Cu 0 concentration combined with abundant Brønsted acid sites, which are responsible for methanol conversion and MF selectivity, respectively. This work provides new insights into the synergy between Cu 0 species and surface acidity of Cu x /CZ5 catalysts for methanol dehydrogenation and offers a feasible and effective strategy for enhancement of the catalytic performance of copper-based catalysts.
研究领域:
催化化学
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材料科学
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高影响因子
Catalysis Science & Technology
·
2020
·Vol. 10
·期 15
·5149-5162
·
IF 5.721
Tongyang Song,Wei Chen,Yuanyuan Qi,Jiqing Lu,Peng Wu,Xiaohong Li
Achieving high catalytic performance with Cu-based catalysts is crucial for the hydrogenation of CO2-derived ethylene carbonate (EC) to simultaneously yield methanol (MeOH) and ethylene glycol (EG). Although Cu-based catalysts are widely studied for the target reaction, there are still some issues to be clarified. In this study, we prepared a 29.1 wt% Cu/SiO2-MHT catalyst by a modified hydrothermal method and successfully applied it to the hydrogenation of EC. In comparison with its three analogues having similar Cu loading and comparable Cu particle size but prepared by different methods, we found that the catalytic performance of the Cu/SiO2 catalysts, including the activity and the selectivity to MeOH, could be tuned by adjusting the Cu+/(Cu0 + Cu+) ratio via different preparation methods. As a result, the Cu/SiO2-MHT catalyst furnished 89% MeOH yield and 37.6 h−1 turnover frequency. To our best knowledge, these values are one of the highest among all heterogeneous Cu catalysts up to now. The results reveal that a cooperative effect exists between Cu0 and Cu+. When the Cu0 species are sufficient to activate H2, a more favorable formation of MeOH can be achieved with more Cu+ species and greater Cu+ surface areas. Furthermore, a greater amount of Lewis acid on the Cu/SiO2-MHT catalyst is also beneficial for MeOH formation.
研究领域:
化学工程
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催化科学
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高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Wen-Jing Yi,Yongzhen Gao,Jingyi Yang,Xiaotian Zhou,Zhongyi Liu,Meng Zhang
A series of CuCoAl catalysts derived from layered double hydroxides (LDHs) with adjustable Cu/Co ratios were prepared via a facile in situ structure topotactic transformation strategy. The comprehensive characterization results revealed that the introduction of Co element and the confined effect of LDHs jointly promoted the dispersion and stability of Cu species, as well as significantly increased the active specific surface area. Interestingly, Cu 1.5 Co 1.5 Al sample showed the superior performance for furfural (FF) hydrogenation to furfuryl alcohol (FA) under the synergistic effect of Cu 0 and Cu + species, as well as the interaction between Cu species and the support. It allowed for FF conversion of 97.5% and FA selectivity of 99.7% (150 °C, 3 h, 2 MPa initial H 2 pressure, isopropanol as solvent, m(FF):m(catalyst) = 60:1). Moreover, Cu 1.5 Co 1.5 Al displayed the satisfactory reusability, where the activity and selectivity kept stable after six successive recycling runs. Specially, it displayed the promising potential for the scale-up production. Furthermore, the mechanism study based on in situ Fourier transform infrared spectra indicated that the surface exposed Cu 0 species could promote the H 2 adsorption and then rapidly dissociated H 2 into the activated H atoms, whilst Cu + species were the active sites for FF selective hydrogenation in a η 1 (O)-aldehyde adsorption configuration.
研究领域:
催化化学
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材料科学
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高影响因子
ACS Sustainable Chemistry & Engineering
·
2026
·
IF 7.3
Wenjun Zhang,Zijiang Zhao,Yonggang Gang,Xiaosong An,Liboting Gao,Siyi Bao,Xuping Ren,Jun Wang,Jianhua Yan,Hao Zhang
Cu/ZnO/Al2O3 (CZA) catalyst remains the benchmark for methanol synthesis but suffers from active-site sintering and insufficient CO2 activation. In this study, we proposed a dual strategy to enhance and regulate the active sites of CZA: hydrothermal treatment induces Cu–Zn coordination to create high-density Cu–ZnO1–x interfaces that promote CO2 conversion, while subsequent La doping regulates Cu0/Cu+ species to favor methanol selectivity. As a result, the maximum space-time yield (STY) of methanol over the designed CZA&5%La-LRCP (prepared by the ligand-regulated coprecipitation method) catalyst improved significantly from 283.0 gMeOH·kgcat–1·h–1 for the conventional coprecipitation-prepared CZA to 400.4 gMeOH·kgcat–1·h–1 under the tested conditions, surpassing most literature reports on La-doped Cu-based catalysts. Comprehensive characterizations and kinetic studies revealed that high-density Cu–ZnO1–x interfaces enhance CO2 adsorption and activation, while uniformly distributed electron-enriched Cu0/Cu+ species promote H2 dissociation and facilitate formate formation and transformation, together establishing an efficient pathway for CO2 activation and hydrogenation. This study demonstrates a promising strategy for the rational design of CO2hydrogenation catalysts through the synergistic modulation of interfacial structure and electronic properties.
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高影响因子
Journal of Energy Chemistry
·
2026
·
IF 15.6
Xue Ye,Yangzhou Xu,Peipei Zhang,Dongwang Zhu,Zhicheng Chen,Yudong Xia,Fulin Yang,Xinhua Gao,Jie Li
CO 2 hydrogenation to methanol is one of the most promising pathways for emission reduction. Unlike traditional synthesis gas (CO + H 2 ) to methanol, a major challenge is that the activation of inert CO 2 at high temperature will induce the reverse water-gas shift (RWGS) reaction to generate CO, thereby reducing the methanol yield. In this research, a novel catalyst Cu 7 Zn 3 Cr 0.3 was synthesized by the carbon microsphere-assisted sol-gel method, which remarkably achieved a maximum methanol space-time yield of 345.1 g kg cat −1 h −1 under mild conditions (200 °C, 3.0 MPa, and 21600 mL g cat −1 h −1 ). Characterizations combined with theoretical simulations show that Cr doping can affect the crystal structure of ZnO, resulting in the formation of more oxygen vacancies (O V s), and induce Cu to form a stable Cu 0 -O V -Cu + active center at the interface. This active structure efficiently enhances the adsorption and activation of CO 2 , while changing the reaction path to inhibit the production of CO. The results indicate that there is a clear linear relationship between the Cu + and O V s concentration and methanol yield, which could provide experimental references for the development of high-performance catalysts for CO 2 methanol production.
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高影响因子
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