Harmonizing the Electronic Structures of the Adsorbate and Catalysts for Efficient CO 2 Reduction

In CO 2 electroreduction, the critical bottleneck lies in the CO 2 activation which requires high overpotentials. CO 2 activation is related to both the electronic structures of catalysts and those of adsorbates, thus an ideal catalyst should match its electronic structures with those of the adsorbate. Here, we harmonized the electronic structures of the adsorbate and Mn-doped In 2 S 3 nanosheets for efficient CO 2 reduction. The introduction of Mn dopants into In 2 S 3 nanosheets enhanced both the Faradaic efficiency (FE) for carbonaceous products and current density ( j ). At −0.9 V vs RHE, Mn-doped In 2 S 3 nanosheets exhibited a remarkable FE of 92% for carbonaceous product at a high j of 20.1 mA cm –2 . Mechanistic studies revealed that Mn doping enabled the harmonic overlaps between the p orbitals of O atoms and d orbitals of Mn atoms near the conduction band edge of Mn-doped In 2 S 3 nanosheets during the activation of CO 2 . Due to the unique electronic structures of the coadsorbed configurations, Mn-doped In 2 S 3 nanosheets exhibited an energy barrier for CO 2 activation into HCOO* lower than that over pristine In 2 S 3 nanosheets.