Engineering Single-Atom Sites into Pore-Confined Nanospaces of Porphyrinic Metal–Organic Frameworks for the Highly Efficient Photocatalytic Hydrogen Evolution Reaction

作者：Qijie Mo, Li Zhang, Sihong Li, Haili Song, Yanan Fan, Cheng‐Yong Su · 发表于：Journal of the American Chemical Society · 年份：2022 · DOI：10.1021/jacs.2c10801 · 被引用次数：212 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Advanced Photocatalysis Techniques、Electrocatalysts for Energy Conversion

As a type of heterogeneous catalyst expected for the maximum atom efficiency, a series of single-atom catalysts (SACs) containing spatially isolated metal single atoms (M-SAs) have been successfully prepared by confining M-SAs in the pore-nanospaces of porphyrinic metal–organic frameworks (MOFs). The prepared MOF composites of M-SAs@Pd-PCN-222-NH 2 (M = Pt, Ir, Au, and Ru) display exceptionally high and persistent efficiency in the photocatalytic hydrogen evolution reaction with a turnover number (TON) of up to 21713 in 32 h and a beginning/lasting turnover frequency (TOF) larger than 1200/600 h –1 based on M-SAs under visible light irradiation (λ ≥ 420 nm). The photo-/electrochemical property studies and density functional theory calculations disclose that the close proximity of the catalytically active Pt-SAs to the Pd–porphyrin photosensitizers with the confinement and stabilization effect by chemical binding could accelerate electron–hole separation and charge transfer in pore-nanospaces, thus promoting the catalytic H 2 evolution reaction with lasting effectiveness.