4.8 Article

Engineering a Self-Grown TiO2/Ti-MOF Heterojunction with Selectively Anchored High-Density Pt Single-Atomic Cocatalysts for Efficient Visible-Light-Driven Hydrogen Evolution

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WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202217439

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Charge Transfer; Heterojunction; MOFs; Photocatalysis; Structure-Activity Relationship

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A photocatalyst TiO2/Ti-BPDC-Pt with a self-grown TiO2/Ti-MOF heterojunction, selectively anchored high-density Pt single-atomic cocatalysts on Ti-BPDC, achieves photocatalytic hydrogen evolution. The intimate heterojunction efficiently separates electrons and holes in a direct Z-scheme, and Pt is selectively anchored on Ti-BPDC in the form of single atoms. The tailored TiO2/Ti-BPDC-Pt exhibits significantly enhanced activity compared to other TiO2- or MOF-based catalysts, showing the importance of the balance of two simultaneously exposed domains of heterojunctions.
A photocatalyst TiO2/Ti-BPDC-Pt is developed with a self-grown TiO2/Ti-metal-organic framework (MOF) heterojunction, i.e., TiO2/Ti-BPDC, and selectively anchored high-density Pt single-atomic cocatalysts on Ti-BPDC for photocatalytic hydrogen evolution. This intimate heterojunction, growing from the surface pyrolytic reconstruction of Ti-BPDC, works in a direct Z-scheme, efficiently separating electrons and holes. Pt is selectively anchored on Ti-BPDC by ligands and is found in the form of single atoms with loading up to 1.8 wt %. The selective location of Pt is the electron-enriched domain of the heterojunction, which further enhances the utilization of the separated electrons. This tailored TiO2/Ti-BPDC-Pt shows a significantly enhanced activity of 12.4 mmol g(-1) h(-1) compared to other TiO2- or MOF-based catalysts. The structure-activity relationship further proves the balance of two simultaneously exposed domains of heterojunctions is critical to fulfilling this kind of catalyst.

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