Engineering Single-Atom Sites into Pore-Confined Nanospaces of Porphyrinic Metal-Organic Frameworks for the Highly Efficient Photocatalytic Hydrogen Evolution Reaction.
Qijie MoLi ZhangSihong LiHaili SongYanan FanCheng-Yong SuPublished in: Journal of the American Chemical Society (2022)
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.
Keyphrases
- metal organic framework
- visible light
- electron transfer
- highly efficient
- density functional theory
- molecular dynamics
- reduced graphene oxide
- photodynamic therapy
- ms ms
- bone mineral density
- gold nanoparticles
- systematic review
- postmenopausal women
- sensitive detection
- transcription factor
- molecularly imprinted
- radiation therapy
- radiation induced
- dna binding
- binding protein