An In Situ Surface-Enhanced Infrared Absorption Spectroscopy Study of Electrochemical CO 2 Reduction: Selectivity Dependence on Surface C-Bound and O-Bound Reaction Intermediates

作者：Yu Katayama, Francesco Nattino, Livia Giordano, Jonathan Hwang, Reshma R. Rao, Oliviero Andreussi, Nicola Marzari, Yang Shao‐Horn · 发表于：The Journal of Physical Chemistry C · 年份：2018 · DOI：10.1021/acs.jpcc.8b09598 · 被引用次数：318 · 研究领域：CO2 Reduction Techniques and Catalysts、Ionic liquids properties and applications、Electrocatalysts for Energy Conversion

The CO 2 electroreduction reaction (CO2RR) is a promising avenue to convert greenhouse gases into high-value fuels and chemicals, in addition to being an attractive method for storing intermittent renewable energy. Although polycrystalline Cu surfaces have long been known to be unique in their capabilities of catalyzing the conversion of CO 2 to higher-order C1 and C2 fuels, such as hydrocarbons (CH 4, C 2 H 4, etc.) and alcohols (CH 3 OH, C 2 H 5 OH), product selectivity remains a challenge. Rational design of more selective catalysts would greatly benefit from a mechanistic understanding of the complex, multiproton, and multielectron conversion of CO 2 . In this study, we select three metal catalysts (Pt, Au, Cu) and apply in situ surface enhanced infrared absorption spectroscopy (SEIRAS) and ambient-pressure X-ray photoelectron spectroscopy (APXPS), coupled to density-functional theory (DFT) calculations, to get insight into the reaction pathway for the CO2RR. We present a comprehensive reaction mechanism for the CO2RR and show that the preferential reaction pathway can be rationalized in terms of metal–carbon (M–C) and metal–oxygen (M–O) affinity. We show that the final products are determined by the configuration of the initial intermediates, C-bound and O-bound, which can be obtained from CO 2 and (H)CO 3, respectively. C1 hydrocarbons are produced via OCH 3,ad intermediates obtained from O-bound CO 3,ad and require a catalyst with relatively high affinity for O-bound i...