中山大学苏成勇团队报道了在卟啉金属-有机框架的孔限纳米空间中工程单原子位点，用于高效光催化析氢反应。相关研究成果发表在2022年11月25日出版的《美国化学会杂志》。

作为一种有望获得最大原子效率的多相催化剂，通过将M-SAs限制在卟啉金属-有机框架（MOFs）的孔纳米空间中，成功制备了一系列含有空间隔离金属单原子（M-SAs）的单原子催化剂（SACs）。制备的MOF复合材料M-SAs@Pd-PCN-222-NH2（M=Pt、Ir、Au和Ru）在光催化析氢反应中表现出极高的持续效率，基于可见光照射下的M-SAs（λ≥ 420nm），在32小时内的转换数（TON）高达21713，开始/持续转换频率（TOF）大于1200/600 h^–1。

光/电化学性质研究和密度泛函理论计算揭示了催化活性Pt-SAs与Pd–卟啉光敏剂的紧密接近，以及化学结合的限制和稳定效应，从而促进持续有效的催化析氢反应。

附：英文原文

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

Author: Qijie Mo, Li Zhang, Sihong Li, Haili Song, Yanan Fan, Cheng-Yong Su

Issue&Volume: November 25, 2022

Abstract: 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-NH2 (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 H2 evolution reaction with lasting effectiveness.

DOI: 10.1021/jacs.2c10801

Source: https://pubs.acs.org/doi/10.1021/jacs.2c10801