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Upgrading CO 2 to formate systems is a promising avenue for fuel production, and SnO x is a unique low-cost candidate for this conversion. However, the high oxygen affinity of Sn sites leads to a strong adsorption of O-bound intermediates, resulting in a low efficiency of CO 2 reduction. Herein, density functional theory (DFT) calculations confirmed that a H-doping strategy of SnO 2 produces partially depleted positive charge Sn sites, weakening the adsorption of HCOO* and boosting the electron transfer kinetics. Experimentally, H-doped commercial SnO 2 nanoparticles (H-SnO 2 ) indeed had enhanced intrinsic activity for CO 2 -to-formate conversion with suppressed hydrogen evolution performance. Remarkably, H-SnO 2 achieves over 90.0% formate selectivity within −0.6 to −1.0 V (vs RHE) at the industrial current density of 220 mA cm −2 . Electrochemical measurements and in situ Raman spectra analysis together disclosed that H-doping speeds up the kinetic rate for the first electron transfer of CO 2 reduction and also promotes formate desorption, resulting in the impressively high current density and selectivity of H-SnO 2 .

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