Metal-Organic Framework Derived Bi-O-Sn/C Nanostructure: Tailoring the Adsorption Site of Dominant Intermediate for Highly Efficient CO Electroreduction to Formate.

Electrochemical CO reduction into high-value-added formic acid/formate is an attractive strategy to mitigate global warming and achieve energy sustainability. However, the adsorption energy of most catalysts for the key intermediate *OCHO is usually weak, and how to rationally optimize the adsorption of *OCHO is challenging. Here, an effective Bi-Sn bimetallic electrocatalyst (Bi -O-Sn @C) where a Bi-O-Sn bridge-type nanostructure is constructed with O as an electron bridge is reported. The electronic structure of Sn is precisely tuned by electron transfer from Bi to Sn through O bridge, resulting in the optimal adsorption energy of intermediate *OCHO on the surface of Sn and the enhanced activity for formate production. Thus, the Bi -O-Sn @C exhibits an excellent Faradaic efficiency (FE) of 97.7% at -1.1 V (vs RHE) for CO reduction to formate (HCOO ) and a high current density of 310 mA cm at -1.5 V, which is one of the best results catalyzed by Bi- and Sn-based catalysts reported previously. Impressively, the FE exceeds 93% at a wide potential range from -0.9 to -1.4 V. In-situ ATR-FTIR, in-situ Raman, and DFT calculations confirm the unique role of the bridge-type structure of Bi-O-Sn in highly efficient electrocatalytic reduction of CO into formate.