Synthesis of Cu/CeO2-x Nanocrystalline Heterodimers with Interfacial Active Sites To Promote CO2 Electroreduction

被引:164
作者
Varandili, Seyedeh Behnaz [1 ]
Huang, Jianfeng [1 ]
Oveisi, Emad [2 ]
De Gregorio, Gian Luca [1 ]
Mensi, Mounir [3 ]
Strach, Michal [1 ]
Vavra, Jan [1 ]
Gadiyar, Chethana [1 ]
Bhowmik, Arghya [4 ]
Buonsanti, Raffaella [1 ]
机构
[1] Ecole Polytech Fed Lausanne, Inst Chem Sci & Engn ISIC, Lab Nanochem Energy LNCE, CH-1950 Sion, Switzerland
[2] Ecole Polytech Fed Lausanne, Interdisciplinary Ctr Electron Microscopy CIME, CH-1015 Lausanne, Switzerland
[3] Ecole Polytech Fed Lausanne, Inst Chem Sci & Engn ISIC, CH-1950 Sion, Switzerland
[4] Tech Univ Denmark DTU, Dept Energy & Convers Storage, DK-2800 Lyngby, Denmark
基金
欧洲研究理事会;
关键词
synthesis design; interfaces; colloidal nanocrystals; electrochemical CO2; reduction; copper; ceria; ELECTROCHEMICAL REDUCTION; CARBON-DIOXIDE; CATALYTIC-ACTIVITY; COPPER-CERIA; CU; SELECTIVITY; TRENDS; OXYGEN; METHANOL; CEO2;
D O I
10.1021/acscatal.9b00010
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Synergistic effects at metal/metal oxide interfaces often give rise to highly active and selective catalytic motifs. So far, such interactions have been rarely explored to enhance the selectivity in the electrochemical CO2 reduction reaction (CO2RR). Herein, Cu/CeO2-x, heterodimers (HDs) are synthesized and presented as one of the prime examples where such effects promote CO2RR, A colloidal seeded-growth synthesis is developed to connect the two highly mismatched domains (Cu and CeO2-x) through an interface. The Cu/CeO2-x HDs exhibit state-of-the-art selectivity toward CO2RR (up to similar to 80%) against the competitive hydrogen evolution reaction (HER) and high faradaic efficiency for methane (up to similar to 54%) at -1.2 V-RHE, which is similar to 5 times higher than that obtained when the Cu and CeO2-x nanocrystals are physically mixed. Operando X-ray absorption spectroscopy along with other ex-situ spectroscopies evidences the partial reduction of Ce4+ to Ce3+ in the HDs during CO2RR A Density Functional Theory (DFT) study of the active site motif in reducing condition reveals synergistic effects in the electronic structure at the interface. The proposed lowest free energy pathway utilizes an O-vacancy site with intermediates binding to both Cu and Ce atoms, a configuration which allows one to break the CHO*/CO* scaling relation. The suppression of HER is attributed to the spontaneous formation of CO* at this interfacial motif and subsequent blockage of the Cu-sites.
引用
收藏
页码:5035 / 5046
页数:23
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