Co2 and h2o coadsorption and reaction on the low-index surfaces of tantalum nitride: A first-principles dft-d3 investigation

A comprehensive mechanistic insight into the photocatalytic reduction of CO2 by H2O is indispensable for the development of highly efficient and robust photocatalysts for artificial photosynthesis. This work presents first-principles mechanistic insights into the adsorption and activation of CO2 in the absence and presence of H2O on the (001), (010), and (110) surfaces of tantalum nitride (Ta3N5), a photocatalysts of significant technological interest. The stability of the different Ta3N surfaces is shown to dictate the strength of adsorption and the extent of activation of CO2 and H2O species, which bind strongest to the least stable Ta3N5(001) surface and weakest to the most stable Ta3N5(110) surface. The adsorption of the CO2 on the Ta3N5(001), (010), and (110) surfaces is demonstrated to be characterized by charge transfer from surface species to the CO2 molecule, resulting in its activation (i.e., forming negatively charged bent CO2^−δ species, with elongated C–O bonds confirmed via vibrational frequency analyses). Compared to direct CO2 dissociation, H2O dissociates spontaneously on the Ta3N5 surfaces, providing the necessary hydrogen source for CO2 reduction reactions. The coadsorption reactions of CO2 and H2O are demonstrated to exhibit the strongest attractive interactions on the (010) surface, giving rise to proton transfer to the CO2 molecule, which causes its spontaneous dissociation to form CO and 2OH⁻ species. These results demonstrate that Ta3N5, a narrow bandgap photocatalyst able to absorb visible light, can efficiently activate the CO2 molecule and photocatalytically reduce it with water to produce value-added fuels.