There are growing interests in metal-free heteroatom-doped carbons for electrochemical CO2 reduction. Previous studies extensively focus on the effect of N-doping, and their products are severely suffered from low current density (mostly <2 mA cm-2) and limited selectivity (<90%). Here, we report that heteroatom codoping offers a promising solution to the above challenge. As a proof of concept, N,P-codoped mesoporous carbon is prepared by annealing phytic-acid-functionalized ZIF-8 in NH3. In CO2-saturated 0.5 M NaHCO3, our catalyst enables CO2 reduction to CO with great selectivity close to ~100% and large CO partial current density (~8 mA cm-2), which are, in our best knowledge, superior to all other relevant competitors. Theoretical simulations show that the improved activity and selectivity are stemmed from the enhanced surface adsorption of *COOH and *CO intermediates as a result of the synergy of N and P codoping.
CO2 reduction, heteroatom codoping, mesoporous carbon, selectivity