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.

An effective strategy for the fabrication of an efficient HER photocatalyst of Pt@Pd-PCN222(Hf) has been reported.

Porous porphyrin metal-organic frameworks (PMOFs) provide promising platforms for studying CO capture and conversion (C3) owing to their versatility in photoelectric, catalytic, and redox activities and porphyrin coordination chemistry. Herein, we report the C3 application of two PMOFs by engineering the coordination space through the introduction of two catalytic metalloporphyrins doped with rhodium or iridium, Rh-PMOF-1 and Ir-PMOF-1, both of which can serve as heterogeneous catalysts for the chemical fixation of CO into cyclic carbonates with yields of up to 99 %. Remarkably, the catalytic reactions can effectively proceed under low CO concentrations and high yields of 83 % and 73 % can be obtained under 5 % CO in the presence of Rh-PMOF-1 and Ir-PMOF-1, respectively. The synergistic effect of the metalloporphyrin ligand and the Zr O cluster, in combination with the CO concentration effect from the pore space, might account for the excellent catalytic performance of Rh-PMOF-1 under low CO concentration. Recycling tests of Rh-PMOF-1 show negligible loss of catalytic activity after 10 runs.

Hydrosilanes are useful precursors for the preparation of many different silicon-containing molecules, and they are transformed into value-added molecules generally through Si–H bond activation. Herein, we report the synthesis of a series of porphyrinic metal–organic framework (MOF) composites that were encapsulated with bimetallic PtCu nanowires (PtCu@Ir-PCN-222) and their catalytic performances toward Si–H bond functionalization. Catalytic results showed that PtCu@Ir-PCN-222 was efficient for the hydrolytic oxidation of hydrosilane and CO2 hydrosilylation. Especially, the turnover number in PtCu@Ir-PCN-222-catalyzed hydrosilane oxidation was up to 27,857 based on Pt. Theoretical studies disclosed that Ir­(III) porphyrin might interact with hydrosilane via a η2-(H–Si) coordination model, and meanwhile, PtCu alloys displayed higher Si–H activation ability than the sole Pt nanoparticles because of the well-tuned Pt and Cu electronic structures in the bimetallic PtCu nanowires.

A facile synthesis of a series of Fe–oxo chain-based porphyrinic MOFs (namely M-PMOF-3(Fe), M = Fe, Co, Ni, Cu) has been reported.