Electroreduction of carbon dioxide to hydrocarbons and oxygenates on copper involves reduction to a carbon monoxide adsorbate followed by further transformation to hydrocarbons and oxygenates. Simultaneous improvement of these processes over a single reactive site is challenging due to the linear scaling relationship of the binding strength of key intermediates. Herein, we report improved electroreduction of carbon dioxide by exploiting a one-pot tandem catalysis mechanism based on computational and electrochemical investigations. By constructing a well-defined copper-modified silver surface, adsorbed carbon monoxide generated on the silver sites is proposed to migrate to surface copper sites for the subsequent reduction to methane, which is consistent with insights gained from operando attenuated total reflectance surface enhanced infrared absorption spectroscopic investigations. Our results provide a promising approach for designing carbon dioxide electroreduction catalysts to enable one-pot reduction of products beyond carbon monoxide and formate.

二氧化碳在铜上的电还原为碳氢化合物和含氧化合物涉及还原为一氧化碳吸附物，然后进一步转化为碳氢化合物和含氧化合物。由于关键中间体的结合强度呈线性比例关系，因此在单个反应位点上同时改进这些方法具有挑战性。在本文中，我们报告了通过基于计算和电化学研究的一锅串联催化机理，改进了二氧化碳的电还原反应。通过构建定义明确的铜修饰的银表面，建议在银位点上产生的吸附一氧化碳迁移到表面铜位点，随后还原为甲烷，这与从操作衰减全反射表面增强红外吸收光谱研究中获得的见解是一致的。我们的结果为设计二氧化碳电还原催化剂提供了一种有前途的方法，以使一氧化碳和甲酸盐以外的产品能够一锅还原。