Photocatalytic HER Performance of TiO₂-supported Single Atom Catalyst Based on Electronic Regulation: A DFT Study

Abstract

Hydrogen is a kind of sustainable clean energy. Sunlight-driven hydrogen evolution reaction(HER) from water splitting assisted by photocatalysts is very crucial for developing clean energy technologies. Single-atom catalysts, such as atomically dispersed Pt on anatase(Pt₁/TiO₂) have exhibited excellent photocatalytic HER performance. However, the role of a single atom is still elusive. The mechanism of photocatalytic HER of TiO₂-supported noble metal single-atom catalysts has been studied. The supported single-atom Pt could narrow the bandgap of TiO₂, enhance the optical absorption properties, and promote the transfer of the excited electrons. Excited electrons do not participate in the process of O-H cleavage, but can participate in the process of proton reduction and greatly reduce the hydrogen evolution energy barrier. Therefore, the hydrogen evolution energy can be used as a descriptor to evaluate the activity of TiO₂-supported single-atom catalysts. The activity of hydrogen evolution is found to be related to the number of d-band electrons of the single noble atom on M₁/TiO₂(M=Pd, Pt, Rh, Ir). The increase of the number of d electrons in the single atom could reduce the hydrogen evolution energy and promote the hydrogen evolution process.

Keywords

TiO₂ / Single-atom catalyst / Photocatalysis / Density functional theory

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