@article{R2025114642,
abstract = {Herein, we have performed DFT＋U calculations to investigate the adsorption and activation of CO2 on a Ta-doped anatase TiO2(101) and compared it to that on a pristine anatase TiO2(101). Replacing Ti with a higher valence Ta-dopant results in an excess electron, which localizes on the neighboring Ti atom. We find that there is a slight increase in adsorption energy of CO2 with Ta-doping, however, there is no significant change in the barriers for CO2 activation. Further, presence of a water molecule enhances the adsorption energy and stabilizes the CO2 molecule having both linear and bent configurations (activated). This stabilization is more pronounced for a activated CO2 molecule, which is attributed to the strong H-bonding. Apart from being a reactant, water also acts as a co-catalyst and significantly reduces the barrier for CO2 activation. This is true for both anatase TiO2(101) and Ta-doped anatase TiO2(101). We have also investigated the activation of CO2 via hydrogen and two electron transfer, which constitutes the limiting step in the photochemical reduction of CO2 to CH4. Our calculations show that the barriers for CO2 activation via the two-electron pathway are similar for both anatase TiO2(101) and Ta-doped TiO2(101). However, presence of a water molecule on Ta-doped TiO2(101), not only stabilizes the CO2 molecule but also reduces the barrier for CO2 activation dramatically by acting as a co-catalyst.},
author = {Nikil Surya R. and Raju Kumar Gupta and Vishal Agarwal},
title = {Modeling the role of Ta-dopant and co-catalytic water for activation of CO2 on anatase TiO2(101)},
journal = {Molecular Catalysis},
volume = {570},
pages = {114642},
year = {2025},
issn = {2468-8231},
doi = {https://doi.org/10.1016/j.mcat.2024.114642},
url = {https://www.sciencedirect.com/science/article/pii/S2468823124008241},
}