Harmonizing The Electronic Structures Of Catalysts And The Adsorbate For Efficient CO₂ Reduction

The ever-increasing energy consumption and the shortage of fossil fuels actuate the exploration of sustainable alternatives to long-term energy supply.One engaging approach is the electroreduction of CO2 into high value-added fuels which store the renewable electricity and simultaneously assuages the rising concentration of CO2.In CO2 electroreduction,the efficiency is predominantly limited by the high energy barrier of CO2 activation which requires a high overpotential of-1.9 V vs RHE.Given that CO2 activation is related to both those of adsorbates and the electronic structures of catalysts,thusly an ideal catalyst should match electronic structures with those of adsorbates.Herein,we harmonized the electronic structures of Mn-doped In2S3 nanosheets and the adsorbate for efficient CO2 electroreduction.The introduction of Mn doping into In2S3 nanosheets improved both current density(j)and the Faradaic efficiency(FE)for carbonaceous product.Mn-doped In2S3 nanosheets exhibited a high j of 42.1 mA cm-2 and a outstanding FE of 96%for carbonaceous product at-1.0 V vs RHE.Mechanistic studies indicated that Mn dopant enabled the harmonic overlaps between the d orbitals of Mn atoms and p orbitals of O atoms near the conduction band edge of Mn-doped In2S3 nanosheets in the time of the activation of CO2.Mn-doped In2S3 nanosheets presented a lower energy barrier for CO2 activation into HCOO*intermediate compared with that over pristine In2S3 nanosheets as a result of the exclusive electronic structures of the co-adsorbed configurations.