N and OH-Immobilized Cu3 Clusters In Situ Reconstructed from Single-Metal Sites for Efficient CO2 Electromethanation in Bicontinuous Mesochannels

被引:37
作者
Pan, Fuping [4 ,5 ]
Fang, Lingzhe [1 ]
Li, Boyang [2 ]
Yang, Xiaoxuan [3 ]
O'Carroll, Thomas [3 ]
Li, Haoyang [4 ]
Li, Tao [1 ,6 ]
Wang, Guofeng [2 ]
Chen, Kai-Jie [4 ]
Wu, Gang [3 ]
机构
[1] Northern Illinois Univ, Dept Chem & Biochem, De Kalb, IL 60115 USA
[2] Univ Pittsburgh, Dept Mech Engn & Mat Sci, Pittsburgh, PA 15261 USA
[3] Univ Buffalo State Univ New York, Dept Chem & Biol Engn, Buffalo, NY 14260 USA
[4] Northwestern Polytech Univ, Sch Chem & Chem Engn, Xian 710072, Shaanxi, Peoples R China
[5] Northwestern Polytech Univ, Chongqing Innovat Ctr, Chongqing 401135, Peoples R China
[6] Argonne Natl Lab, Xray Sci Div, Chem & Mat Sci Grp, Lemont, IL 60439 USA
基金
中国国家自然科学基金; 美国国家科学基金会;
关键词
CARBON-DIOXIDE; ATOM CATALYSTS; ELECTROCATALYTIC REDUCTION; ELECTROCHEMICAL REDUCTION; GENERAL-SYNTHESIS; OXYGEN REDUCTION; ELECTROREDUCTION; IDENTIFICATION; CHALLENGES; CONVERSION;
D O I
10.1021/jacs.3c10524
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Cu-based catalysts hold promise for electrifying CO2 to produce methane, an extensively used fuel. However, the activity and selectivity remain insufficient due to the lack of catalyst design principles to steer complex CO2 reduction pathways. Herein, we develop a concept to design carbon-supported Cu catalysts by regulating Cu active sites' atomic-scale structures and engineering the carbon support's mesoscale architecture. This aims to provide a favorable local reaction microenvironment for a selective CO2 reduction pathway to methane. In situ X-ray absorption and Raman spectroscopy analyses reveal the dynamic reconstruction of nitrogen and hydroxyl-immobilized Cu-3 (N,OH-Cu-3) clusters derived from atomically dispersed Cu-N-3 sites under realistic CO2 reduction conditions. The N,OH-Cu-3 sites possess moderate *CO adsorption affinity and a low barrier for *CO hydrogenation, enabling intrinsically selective CO2-to-CH4 reduction compared to the C-C coupling with a high energy barrier. Importantly, a block copolymer-derived carbon fiber support with interconnected mesopores is constructed. The unique long-range mesochannels offer an H2O-deficient microenvironment and prolong the transport path for the CO intermediate, which could suppress the hydrogen evolution reaction and favor deep CO2 reduction toward methane formation. Thus, the newly developed catalyst consisting of in situ constructed N,OH-Cu-3 active sites embedded into bicontinuous carbon mesochannels achieved an unprecedented Faradaic efficiency of 74.2% for the CO2 reduction to methane at an industry-level current density of 300 mA cm(-2). This work explores effective concepts for steering desirable reaction pathways in complex interfacial catalytic systems via modulating active site structures at the atomic level and engineering pore architectures of supports on the mesoscale to create favorable microenvironments.
引用
收藏
页码:1423 / 1434
页数:12
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