Exploring the Role of La Codoping beyond Charge Compensation for Enhanced Hydrogen Evolution by Rh–SrTiO3

In this theoretical study, we investigate recent observation of enhancement of hydrogen evolution efficiency of Rh-doped SrTiO3 due to codoping with La at the Sr lattice site. Using hybrid density functional theory, we have systematically studied the electronic structure of (Rh, La)-codoped SrTiO3 and compared with that of Rh-doped SrTiO3, La-doped SrTiO3, and undoped SrTiO3. The aim of the present study has been to explore the role of different factors toward the observed enhanced photoactivity of (Rh, La)-codoped SrTiO3. Doping with only Rh significantly reduces the photoabsorption energy by introducing localized acceptor states between the valence band and conduction band. Unfortunately, these states act as efficient sources for charge carrier trapping. Besides, the oxygen vacancy found to be present in the Rh-doped SrTiO3 as a charge compensating defect also accelerates the electron-hole recombination rate. We have shown that codoping with La and Rh leads to the formation of clean band structure without encountering any midgap states. Introduction of La into the Rh-doped SrTiO3 not only reduces the quantity of Rh(4+) species but also suppresses the oxygen vacancy due to formation of a charge-compensated system. The presence of La favors Rh doping into the crystal structure of SrTiO3 by reducing the formation energy. Moreover, the conduction band minima are found to be shifted in the upward direction significantly due to codoping with Rh and La, thereby increasing the reducing behavior at the conduction band. This leads to enhancement of hydrogen evolution activity of SrTiO3 during photocatalytic water splitting under visible light.