JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2026
·
IF 9.6
Yue Shen,Jielian Yang,Bing Chen,Chunyan Zhou,Liya Zhou,Binbin Luo,Qi Pang,Peican Chen,Xuetang Xu,Anxiang Guan
Developing efficient electrocatalysts capable of achieving effective electrochemical CO 2 -to-CH 4 conversion over a broad potential window remains a significant challenge in the field. Herein, we present a facile strategy for the synthesis of inverse CeO 2 /CuO catalysts through a hydrothermal approach, wherein CeO 2 nanodomains are supported on the surface of CuO. This catalyst exhibits exceptionally high CH 4 selectivity across the investigated voltage range, with a peak Faradaic efficiency of 63.6% and a corresponding partial current density of −472.9 mA cm −2 at −1.6 V vs. RHE, while the pure CuO catalyst without CeO 2 component was found to be active for electroreducing CO 2 to C 2+ products (C 2 H 4 ), as the adjacent Cu sites were beneficial for adsorbing multiple *CO intermediates and subsequent C C coupling. The incorporation of CeO 2 into Cu 1 Ce 9 -O x exerts a dual regulatory effect, synergistically suppressing C C coupling by reducing *CO coverage and optimizing *CO protonation kinetics for enhanced CH 4 selectivity. The presence of CeO 2 not only blocks the active sites of CuO for CO 2 -to-*CO intermediate conversion (thus lowering *CO coverage) but also facilitates water dissociation to generate abundant *H species, which subsequently migrate to Cu sites in Cu 1 Ce 9 -O x catalyst through the coherent interface between CuO and CeO 2 . These *H species subsequently facilitate the hydrogenation of *CO intermediates, ultimately resulting in CH 4 formation. Density functional theory (DFT) calculations demonstrate that CuCe-O x catalyst with strong H 2 O dissociation capability decreases the energy barrier for *CHO formation and favors *CO → *CHO conversion, thereby promoting CO 2 RR-to-CH 4 conversion. This work provides an effective strategy to enhance *H generation and the hydrogenation of *CO intermediates, thereby offering a feasible approach to improve CH 4 production efficiency in electrochemical CO 2 conversion. Compared with pristine CuO, CeO 2 nanodomains anchored on CuO surfaces redirect CO 2 electroreduction selectivity from C 2 H 4 to CH 4 . The presence of CeO 2 not only modulate *CO intermediate coverage but also accelerate H 2 O dissociation to produce abundant *H species, thereby promoting *CO protonation and boosting CH 4 formation with enhanced Faradaic efficiency. Download: Download high-res image (170KB) Download: Download full-size image
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Green Energy & Environment
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2026
·
IF 14.6
Lijun Xiong,Dandan Zhu,Chenglong Qiu,Weihong Zeng,Mingshi Xu,Shanshan Wang,Yong Yang
The photocatalytic reduction of carbon dioxide (CO 2 ) into high-value C 2+ hydrocarbons represents a sustainable pathway to alleviate energy shortages and reduce atmospheric CO 2 levels. In this study, a unique tandem photocatalyst (CoTi-CN), is constructed by integrating bimetallic CoTi-MOF with metal-free half-metallic C(CN) 3 . This composite demonstrates markedly enhanced activity and selectivity in the photocatalytic CO 2 reduction to ethylene (C 2 H 4 ), achieving a C 2 H 4 selectivity of 36.8% and a generation yield of 31.3 μmol g −1 over 5 h. Density functional theory (DFT) calculations combined with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis reveal that C(CN) 3 acts as an efficient CO 2 to CO converter, while CoTi-MOF favors the adsorption and C-C coupling of *CO intermediates. The spatially decoupled CO generation and C-C coupling processes lead to optimized intermediate coverage and reduced energy barriers, resulting in superior selectivity toward multi-carbon products. This work opens new horizons for the design of tandem photocatalysts that combine half-metallic catalysts with bimetallic MOFs, achieving a significant enhancement in the activity and selectivity of photocatalytic C 2 H 4 production.
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Lu Gao,Yue Zhou,Lulu Li,Lin Chen,Luwei Peng,Jinli Qiao,Feng F. Hong
A CNT/Bacterial Cellulose (BC) nanocomposite with a large surface area and conductive properties was in-situ cultivated to retain the native 3D nanofibril network. The Cu-Cu x O/CNT/BC nanocomposite electrode was in-situ fabricated via reduction with the CNT/BC composite as a support, comparing KBH 4 and NaBH 4 as a reducing agent to obtain efficient electrodes for CO 2 reduction (ECR-CO 2 ). Both electrodes exhibited higher performance than the traditional carbon cloth or pristine BC supported Cu-based catalysts for conversion of ECR-CO 2 to CO and C 2 H 4 . The CNT/BC as a support provided not only more active sites for copper catalyst but also increased the charge transfer and selective performance of C 2 H 4 product, due to the synergistic effect of CNT and copper. The smaller honeycomb and dendritic lamellar crystal morphology of the obtained Cu-Cu x O/CNT/BC NaBH4 electrode possessed a large electrochemical specific surface area, providing more active sites for ECR-CO 2 . The double-layer capacitance and the current density reached 11.8 mF cm −2 and 33.3 mA cm −2 , respectively. At a potential of −1.5 V RHE , the Faraday efficiency (FE CO + FE C2H4 ) was 66%. Moreover, the Cu-Cu x O/CNT/BC nanocomposite electrode was very stable, and withstood tolerance in ECR-CO 2 for more than 20 h. This study possibly will provide a new design for catalyst support on CNT/BC substrate to regulate advanced catalysts/electrodes for different applications, especially to ECR-CO 2 in terms of higher charge transport properties, lower contact resistance, higher current density, and more stable CO 2 electroreduction performance.
研究领域:
材料科学
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电化学
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环境科学
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Research
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2022
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IF 11.036
Jin-Meng Heng,Hao-Lin Zhu,Zhen-Hua Zhao,Da-Shuai Huang,Jun-Yi Li,Pei-Qin Liao,Xiao-Ming Chen
Inorganic solids are a kind of important catalysts, and their activities usually come from sparse active sites, which are structurally different from inactive bulk. Therefore, the rational optimization of activity depends on studying these active sites. Copper is a widely used catalyst and is expected to be a promising catalyst for the electroreduction of CO2 to C2H4. Here, we report a conductive dinuclear cuprous complex with a short Cu···Cu contact for the electroreduction of CO2 to C2H4. By using 1H-[1,10]phenanthrolin-2-one and Cu(I) ions, a dinuclear cuprous complex [Cu2(ophen)2] (Cuophen) with a remarkable conductivity (3.9 × 10−4 S m−1) and a short intramolecular Cu···Cu contact (2.62 Å) was obtained. Such a short Cu···Cu contact is close to the distance of 2.54 Å between 2 adjacent Cu atoms in the edge of the copper(100)/(111) plane. Detailed examination of Cuophen revealed a high activity for the electroreduction of CO2 to C2H4 with a Faradaic efficiency of 55(1)% and a current density of 580 mA cm−2, and no obvious degradation was observed over 50 h of continuous operation. Comparing the properties and mechanisms of Cuophen and 2 other copper complexes with different Cu···Cu distances, we found that the shorter Cu···Cu distance is conducive not only for a *CO species to bridge 2 copper ions into a more stable intermediate transition state but also for C–C coupling.
研究领域:
无机化学
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电催化
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材料科学
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能源转换
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高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
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2019
·Vol. 25
·期 38
·9052-9059
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IF 5.16
Jiahui Liu,Guoying Zhao,Ocean Cheung,Lina Jia,Zhenyu Sun,Suojiang Zhang
Graphical Biomimetic heterogeneous catalysts : Multifunctional metalloporphyrin covalent ionic frameworks with a highly porous structure for cooperative catalysis by Lewis acidic metal sites and nucleophilic Br − ions showed efficient catalytic activity in CO 2 cycloaddition to epoxides (see figure), and the catalytic performance could be further enhanced by altering the functional groups and the BET surface area. The development of multifunctional heterogeneous catalysts with high porosity and remarkable catalytic activity still remains a challenge. Herein, four highly porous metalloporphyrin covalent ionic frameworks (CIFs) were synthesized by coupling 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin (TNPP) with 3,8-diamino-6-phenylphenanithridine (NPPN) or 5,5′-diamino-2,2′-bipyridine (NBPy) followed by ionization with bromoethane (C 2 H 5 Br) or dibromoethane (C 2 H 4 Br 2 ) and then metalization with Zn or Co. The resulting CIFs showed high efficiency in catalyzing the cycloaddition of propylene oxide (PO) with CO 2 to form propylene carbonate (PC). All of the Zn-containing CIF catalysts were able to catalyze the cycloaddition reaction with a PC yield greater than 97 %. The TNPP/NBPy (CIF2) catalyst ionized with C 2 H 4 Br 2 and metalized with Zn (Zn-CIF2-C 2 H 4 ) exhibited the highest catalytic activity among the synthesized catalysts. The high catalytic performance of Zn-CIF2-C 2 H 4 is related to its high porosity (577 m 2 g −1 ), high Br:metal ratio (1:3.89), and excellent synergistic action between the Lewis acidic Zn sites and the nucleophilic Br − ions. Zn-CIF2-C 2 H 4 is sufficiently stable that greater than 94 % PC yield could be obtained even after six cycles. In addition, Zn-CIF2-C 2 H 4 could catalyze the cycloaddition of several other epoxides with CO 2 . These highly porous materials are promising multifunctional and efficient catalysts for industrially relevant reactions.
研究领域:
催化
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材料科学
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化学
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环境科学
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工业化学
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高影响因子
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