CO$_2$ adsorption and photocatalytic reduction mechanisms on Ti-terminated CaTiO$_3$ (100) surface: a DFT study (2504.19297v1)

Abstract: Photoreduction of CO$2$ is an important alternative approach aimed to reduce the CO$_2$ atmospheric content which is responsible of the global warming. The development of an efficient photocatalyst can strongly improve the efficiency and selectivity of the by-products of such a process. Recently, CaTiO$_3$ has been used as an alternative semiconductor catalyst due to its attractive properties. In this study, we use calculations of the electronic structure of first principles to investigate for the first time the general reaction mechanism that leads to the main value-added by-products of HCOOH, CO, H$_3$COH and CH$_4$ byproducts, focusing on the reactions of adsorption, activation and reduction reactions of CO$_2$ molecules on the Ti-terminated CaTiO$_3$ (100) surface. We compute adsorption energies of the various intermediate configurations and activation energy barriers of the chemical reaction pathways. Our results show that CO$_2$ can be activated by charge transfer of excess electrons leading to a CO$_2$ anion that probably gives HCOO by the first reduction; however, the second hydrogenation to HCOOH is impeded by the prohibitive energy barrier. In particular, activated CO$_2$ can also easily undergo decomposition, which facilitates CO production. Afterwards, we discuss the possible reaction mechanisms of CO photoreduction towards H$_3$COH and CH$_4$ value-added products, taking into account the experimental evidence that only CO and CH$_4$ have been detected. The reaction pathway generally follows the most energetically convenient routes characterized by activated intermediates. Even though H$_3$COH could be finally produced, its strong adsorption ($E{ads}$ of -0.93 eV) and its promoted decomposition to H$3$CO+H on the surface could explain why it has not been detected, as opposed to CH$_4$ whose $E{ads}$ is only -0.22 eV due to its non-polar nature.