Orbital-Tailored Pt Sites via Atomic-Level Carrier Pre-Design for Enhanced Photocatalytic Hydrogen Evolution.
basic_science · Level V
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- Record sourced from PubMed, PMID 41185622.
- Also identified by DOI 10.1021/acsnano.5c16095.
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Abstract
Modulating the coordination geometry of single atoms (SAs) is crucial for overcoming the limitations in catalytic activity. This study aims to construct a clear relationship between the coordination geometry of Pt SAs and their catalytic activity to guide the synthesis of targeted high-activity SA catalysts. An interesting atomic-level predesign strategy for SA carriers is proposed, enabling precise atomic regulation of N<sub>2c</sub> coordination sites. Seven distinct SA carriers were synthesized: pristine CN, N<sub>v</sub>-CN (1, 2, 3) with N<sub>2c</sub> vacancies and O<sub>d</sub>-CN (1, 2, 3), in which N<sub>2c</sub> sites are substituted by oxygen doping, thereby achieving the controlled synthesis of four Pt coordination geometries: Pt-N<sub>4</sub> in pristine CN, Pt-N<sub>2</sub>Cl<sub>4</sub> (reconstructed to Pt-N<sub>2</sub>) in N<sub>v</sub>-CN, and Pt-N<sub>3</sub>O in O<sub>d</sub>-CN. Among these, O<sub>d</sub>-CN-Pt exhibited exceptional photocatalytic hydrogen evolution performance (66.4 mmol g<sup>-1</sup> h<sup>-1</sup>), which is 3.75 and 2.7 times higher than that of CN-Pt and N<sub>v</sub>-CN-Pt, respectively. By combining <i>in-situ</i> KPFM-SPV, X-ray photoelectron spectroscopy, femtosecond transient absorption, and density functional theory calculations, a volcano-type relationship model was established between activity and three descriptors Bader charge, Pt 5d intensity, and Δ<i>E</i> (from PDOS to the Fermi level)─to elucidate the correlation between the coordination geometry and catalytic activity of SA-based catalysts. Such a descriptor may guide the predesign of high-performance SA catalysts.