Weakened Interfacial Hydrogen Bond Connectivity Drives Selective Photocatalytic Water Oxidation toward H2O2 at Water/Brookite-TiO2 Interface.
J Am Chem Soc
; 146(9): 6084-6093, 2024 Mar 06.
Article
en En
| MEDLINE
| ID: mdl-38386422
ABSTRACT
The formation of H2O2 through the two-electron photocatalytic water oxidation reaction (WOR) is significant but encounters the competition with the four-electron O2 evolution reaction. Recent studies showed a crystal-phase dependence in H2O2 selectivity, where high purity brookite TiO2 (b-TiO2) exhibits remarkable H2O2 selectivity in contrast to the common rutile phase TiO2 (r-TiO2). However, the origin of such a structure-induced selectivity preference remains elusive, primarily due to the complexities associated with the solid-liquid interface system and excited-state chemistry. Herein, we conducted a comprehensive investigation into the selectivity mechanism of WOR at the water/b-TiO2(210) and water/r-TiO2(110) interfaces, employing first-principles molecular dynamics simulations and microkinetic analyses. Intriguingly, our results reveal that the intrinsic catalytic ability of the b-TiO2(210) itself does not enhance H2O2 selectivity compared to r-TiO2(110). Instead, it is the weakened interfacial hydrogen bond connectivity, modulated by the herringbone-like local atomic structure of the b-TiO2(210) surface, that determines the selectivity. Specifically, this weakened H-bond connectivity (i.e., local low water density) at the interface, owing to the strong water adsorption and distinct adsorption orientation, can stabilize the OH⢠radical and inhibit its deprotonation, leading to an improved H2O2 selectivity. By contrast, the relatively strong interface H-bond connectivity established over r-TiO2(110) accelerates the deprotonation of OHâ¢, with the OH⢠coverage being 3 orders of magnitude lower than at the water/b-TiO2(210) interface. This study quantitatively demonstrates that the local H-bond structure (water density) at the liquid/solid interface significantly influences photocatalytic selectivity, and this insight may offer a rational approach to enhance the H2O2 selectivity.
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MEDLINE
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Revista:
J Am Chem Soc
Año:
2024
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Article
País de afiliación:
China