Photocatalytic Behavior of Fluorinated Rutile TiO$_2$(110) Surface: Understanding from the Band Model

TL;DR

This study uses DFT calculations to explain how fluorination of TiO₂ surfaces affects photocatalytic activity by shifting band edges, impacting radical formation and degradation efficiency of organic compounds.

Contribution

It provides a band model-based explanation for fluorination effects on TiO₂ photocatalysis, suggesting strategies to enhance degradation performance.

Findings

Fluorination lowers TiO₂ band edges.

Lowered valence band edge promotes H radical production.

Lowered conduction band edge reduces photo-electron reducing power.

Abstract

Surface fluorination of TiO$_2$ (F-TiO$_2$) has complicate photocatalytic behavior in degradation of organic compounds. This work attempts to establish an elegant scenario based on the band model to understand this behavior. Density functional theory (DFT) calculations show that fluorination of the rutile TiO$_2$(110) surface (F-TiO$_2$${110}$) results in the falling of band edges. The falling of valence band edge (VBE) facilitates production of free $\cdot$OH radicals, whereas the falling of conduction band edge (CBE) lowers the reducing power of photo-electrons and inhibits reductive reactions mediated by them. As a result, the photo-electrons are built up in the conduction band which depresses photo-holes in the valence band to produce $\cdot$OH radicals due to the requirement of electrical neutrality and thus leads to a low degradation rate of organic compounds. Even though, our model suggests a route to improve the degradation efficiency, by introducing a scavenger of photo-electrons to promote formation of $\cdot$OH radicals.