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The electrochemical reduction of CO2 to produce carbon-based fuels and chemicals possesses huge potentials to alleviate current environmental problems. However, it is confronted by great challenges in the design of active electrocatalysts with low overpotentials and high product selectivity. Here we report the atomic tuning of a single-Fe-atom catalyst with phosphorus (Fe-N/P-C) on commercial carbon black as a robust electrocatalyst for CO2 reduction. The Fe-N/P-C catalyst exhibits impressive performance in the electrochemical reduction