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Conversion of CO2 into fuels and chemicals has been considered to be an important strategy to reduce greenhouse gas emissions and alleviate the energy crisis. Bicarbonate as a CO2 source is convenient for experimental operation. Herein, based on the synergistic effect of Ni and ZnO benefitting from the electronic transfer, ultrasmall Ni-ZnO clusters (∼2 nm) stabilized by microporous silica nanoparticles were designed and prepared for catalyzing the hydrogenation of sodium bicarbonate to formic acid. The yield of formic acid reached up to