ACS Catalysis
·
2026
·
IF 13.6
Shi Zhanghan,Duan Fangyu,Liu Yafei,Zhang Xianwang,Song Guoquan,Yang Xiaomeng,Ma Qianli,Zhang Zongwu,Wu Dan,Xu Chunbao,Zhang Yongsheng
Cascade catalytic upgrading of biomass-derived furanic compounds to high-value cyclopentanone (CPO) and cyclopentanol (CPL) over metal–acid bifunctional catalysts has attracted considerable attention in sustainable chemistry. However, conventional bifunctional catalysts exhibit insufficient synergistic effects, primarily due to the lack of flexibility in tuning the ratio of acidic to hydrogenative active sites. Herein, we demonstrate that halogen (Br and Cl) modification of supported Cu catalysts significantly enhances both activity and selectivity in the aqueous-phase hydrogenative rearrangement of furfuryl alcohol (FOL), achieving a CPO yield of 94.4% and a CPL yield of 94.6%, respectively. Extensive characterizations reveal that the electronegative Br and Cl adatoms effectively modulate the electronic state of Cu nanoparticles, facilitating the formation of Lewis acidic Cu + sites on the catalyst surface. Mechanistic investigations disclose that Cu + sites mediate the rearrangement of FOL to 4-hydroxy-2-cyclopentenone (4-HCP), while adjacent Cu 0 sites catalyze the hydrogenation of 4-HCP to CPO, followed by its subsequent hydrogenation to CPL. Different binding strengths between Cu and halogens (I > Br > Cl) allow the regulation of the Cu + /Cu 0 ratio on the Cu surface, which in turn provides an effective way to control the reaction pathway. The developed halogen modification strategy not only offers great potential for the upgrading of biomass-derived furanics to cyclopentane derivatives but also presents a versatile strategy for regulating the surface Lewis acidity of metal catalysts, which is crucial for metal–acid bifunctional catalysis.
✓ 已验证
产品关联
DOI
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.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
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
✓ 已验证
产品关联
DOI
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.
✓ 已验证
产品关联
DOI
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
·
催化科学
✓ 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）