Operando X‑ray Absorption Spectroscopy Study of SnO₂ Nanoparticles for Electrochemical Reduction of CO₂ to Formate

Tin-based electrocatalysts exhibit a remarkable ability to catalyze CO₂ to formate selectively. Understanding the size–property relationships and exploring the evolution of the active size still lack complete understanding. Herein, we prepared SnO₂ nanoparticles (NPs) with a controllable size supported on commercial carbon spheres (SnO₂/C-n, n = 1, 2, and 3) by a simple low-temperature annealing method. The transmission electron microscopy/scanning transmission electron microscopy images and fitting results of the small-angle X-ray scattering profile confirm the increased size of SnO₂ NPs due to the increase of SnO₂ loading. The catalytic performance of SnO₂ has proved the size-dependent effect during the CO₂ reduction reaction process. The as-prepared SnO₂/C-1 displayed the maximum Faradic efficiency of formate (FE_HCOO–) of 82.7% at −1.0 V versus reversible hydrogen electrode (RHE). In contrast, SnO₂/C-2 and SnO₂/C-3 with larger particle sizes achieved lower maximum FE_HCOO– and larger overpotential. Moreover, we employed operando X-ray absorption spectroscopy to study the evolution of the oxidation state and local coordination environment of SnO₂ under working conditions. In addition to the observed shifts of the rising edge of Sn K-edge X-ray absorption near-edge structure spectra to a lower energy side as the applied voltage decreases, the decreased coordination number of Sn in the Sn–O scattering path and the presence of Sn metal contribution in the extended X-ray absorption fine structure spectra verify the reduction of SnO₂ to SnO_x and metallic Sn.