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  Pardo Pérez, L.C.; Teschner, D.; Willinger, E.; Guiet, A.; Driess, M.; Strasser, P.; Fischer, A.: In Situ Formed "Sn_1-xIn_x@In_1-ySn_yO_z" Core@Shell Nanoparticles as Electrocatalysts for CO₂" Reduction to Formate. Advanced Functional Materials 31 (2021), p. 2103601/1-14

10.1002/adfm.202103601
Open Access Version

Abstract:
Electrochemical reduction of CO2 (CO2RR) driven by renewable energy has gained increasing attention for sustainable production of chemicals and fuels. Catalyst design to overcome large overpotentials and poor product selectivity remains however challenging. Sn/SnOx and In/InOx composites have been reported active for CO2RR with high selectivity toward formate formation. In this work, the CO2RR activity and selectivity of metal/metal oxide composite nanoparticles formed by in situ reduction of bimetallic amorphous SnInOx thin films are investigated. It is shown that during CO2RR the amorphous SnInOx pre-catalyst thin films are reduced in situ into Sn1–XInX@In1–YSnYOz core@shell nanoparticles composed of Sn-rich SnIn alloy nanocores (with x < 0.2) surrounded by InOx-rich bimetallic InSnOx shells (with 0.3 < y < 0.4 and z ≈ 1). The in situ formed particles catalyze the CO2RR to formate with high faradaic efficiency (80%) and outstanding formate mass activity (437 A gIn+Sn−1 @ −1.0 V vs RHE in 0.1 m KHCO3). While extensive structural investigation during CO2RR reveals pronounced dynamics in terms of particle size, the core@shell structure is observed for the different electrolysis conditions essayed, with high surface oxide contents favoring formate over hydrogen selectivity.