We report here the
design of two multifunctional metal−organic
frameworks (MOFs), mPT-Cu/Co and mPT-Cu/Re
,
comprising cuprous photosensitizers (Cu-PSs)
and molecular Co or Re catalysts for photocatalytic hydrogen evolution
(HER) and CO2 reduction (CO2RR), respectively.
Hierarchical organization of Cu-PSs and Co/Re catalysts in these MOFs
facilitates multielectron transfer to drive HER and CO2RR under visible light with an HER turnover number (TON) of 18 700
for mPT-Cu/Co and a CO2RR TON of 1328 for mPT-Cu/Re, which represent a 95-fold enhancement over their
homogeneous controls. Photophysical and electrochemical investigations
revealed the reductive quenching pathway in HER and CO2RR catalytic cycles and attributed the significantly improved performances
of MOFs over their homogeneous counterparts to enhanced electron transfer
due to close proximity between Cu-PSs and active catalysts and stabilization
of Cu-PSs and molecular catalysts by the MOF framework.
Catalytic
borylation has recently been suggested as a potential
strategy to convert abundant methane to fine chemicals. However, synthetic
utility of methane borylation necessitates significant improvement
of catalytic activities over original phenanthroline- and diphosphine-Ir
complexes. Herein, we report the use of metal–organic frameworks
(MOFs) to stabilize low-coordinate Ir complexes for highly active
methane borylation to afford the monoborylated product. The mono(phosphine)-Ir
based MOF, Zr-P1-Ir, significantly outperformed other
Ir catalysts in methane borylation to afford CH3Bpin with
a turnover number of 127 at 110 °C. Density functional theory
calculations indicated a significant reduction of activation barrier
for the rate limiting oxidative addition of methane to the four-coordinate
(P1)IrIII(Bpin)3 catalyst to form
the six-coordinate (P1)IrV(Bpin)3(CH3)(H) intermediate, thus avoiding the formation of
sterically encumbered seven-coordinate IrV intermediates
as found in other Ir catalysts based on chelating phenanthroline,
bipyridine, and diphosphine ligands. MOF thus stabilizes the homogeneously
inaccessible, low-coordinate (P1)Ir(boryl)3 catalyst to provide a unique strategy to significantly lower the
activation barrier for methane borylation. This MOF-based catalyst
design holds promise in addressing challenging catalytic reactions
involving highly inert substrates.
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