Simultaneous Generation of H2O2 and Formate by Co‐Electrolysis of Water and CO2 over Bifunctional Zn/SnO2 Nanodots

Hydrogen peroxide (H₂ O₂ ) and formate are important chemicals used in various chemical manufacturing industries. One promising approach for the simultaneous production of these chemicals is coupling anodic two-electron water oxidation with cathodic CO₂ reduction in an electrolyzer using nonprecious bifunctional electrocatalysts. Herein, we report an innovative hybrid electrosynthesis strategy using Zn-doped SnO₂ (Zn/SnO₂ ) nanodots as bifunctional redox electrocatalysts to achieve Faradaic efficiencies of 80.6 % and 92.2 % for H₂ O₂ and formate coproduction, respectively, along with excellent stability for at least 60 h at a current density of ≈150 mA cm^-2 . Through a combination of physicochemical characterizations, including operando attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), isotope labeling mass spectrometry (MS)/¹ H NMR and quasi-in situ electron paramagnetic resonance (EPR), with density functional theory (DFT) calculations, we discovered that the Zn dopant facilitates the coupling of *OH intermediates to promote H₂ O₂ production and optimizes the adsorption of *OCHO intermediates to accelerate formate formation. Our findings offer new insights into designing more efficient bifunctional electrocatalyst-based pair-electrosynthesis system for the coproduction of H₂ O₂ and formate feedstocks.