Ag–Sn Bimetallic Catalyst with a Core–Shell Structure for CO2 Reduction

Converting greenhouse gas carbon dioxide (CO2) to value-added chemicals is an appealing approach to tackle CO2 emission challenges. The chemical transformation of CO2 requires suitable catalysts that can lower the activation energy barrier, thus minimizing the energy penalty associated with the CO2 reduction reaction. First-row transition metals are potential candidates as catalysts for electrochemical CO2 reduction; however, their high oxygen affinity makes them easy to be oxidized, which could, in turn, strongly affect the catalytic properties of metal-based catalysts. In this work, we propose a strategy to synthesize Ag–Sn electrocatalysts with a core–shell nanostructure that contains a bimetallic core responsible for high electronic conductivity and an ultrathin partially oxidized shell for catalytic CO2 conversion. This concept was demonstrated by a series of Ag–Sn bimetallic electrocatalysts. At an optimal SnOx shell thickness of ∼1.7 nm, the catalyst exhibited a high formate Faradaic efficiency of ∼80% and a formate partial current density of ∼16 mA cm–2 at −0.8 V vs RHE, a remarkable performance in comparison to state-of-the-art formate-selective CO2 reduction catalysts. Density-functional theory calculations showed that oxygen vacancies on the SnO (101) surface are stable at highly negative potentials and crucial for CO2 activation. In addition, the adsorption energy of CO2– at these oxygen-vacant sites can be used as the descriptor for catalytic performance because of its linear correlation to OCHO* and COOH*, two critical intermediates for the HCOOH and CO formation pathways, respectively. The volcano-like relationship between catalytic activity toward formate as a function of the bulk Sn concentration arises from the competing effects of favorable stabilization of OCHO* by lattice expansion and the electron conductivity loss due to the increased thickness of the SnOx layer.