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

QJ Mo and L Zhang and SH Li and HL Song and YA Fan and CY Su, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 144, 22747-22758 (2022).

DOI: 10.1021/jacs.2c10801

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 (lambda >= 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.

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