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Regulating Ligand-to-Metal Charge Transfer in UiO-66(Zr)-NH2 With Site-Isolated Cu+ Centers for Efficient Photocatalytic H2O2 Generation
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DOI：10.1002/smsc.70333.png)
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Abstract
En 中文
Site-isolated metal centers within metal-organic frameworks (MOFs) offer a promising strategy to regulate charge–transfer dynamics and enhance photocatalysis. Here, we investigate the influence of atomically dispersed Cu ions on the photophysics and photocatalytic activity of the zirconium-based MOF UiO-66(Zr)-NH2. Cu was incorporated via wet impregnation, producing Cu@UiO-66(Zr)-NH2 composites with preserved crystallinity. Structural and spectroscopic analyses confirm that Cu is stabilized predominantly as site-isolated Cu+ species interacting with the amino-functionalized linker. Photoluminescence studies reveal that Cu incorporation introduces an additional ligand-to-Cu charge–transfer pathway that competes with the intrinsic ligand-to-cluster transfer to the Zr6O4(OH)4 nodes, resulting in strong photoluminescence quenching. Time-resolved photoluminescence and transient infrared spectroscopy demonstrate that Cu sites efficiently capture photogenerated electrons, suppressing energy dissipation and accelerating charge-separation processes. These electronic effects significantly enhance photocatalytic oxygen reduction for H2O2 production under simulated solar irradiation. The H2O2 yield upon using 5 mg of MOF increased from ∼1.5 µmol h−1 for pristine UiO-66(Zr)-NH2 to ∼8.2 µmol h−1 for the 7 wt% Cu-loaded material. Mechanistic investigations indicate Cu+ centers promote oxygen adsorption and activation, favoring the two-electron oxygen reduction pathway. This work demonstrates that site-isolated Cu ions can modulate ligand-to-metal charge–transfer processes in MOFs, offering a rational strategy to design efficient photocatalysts.
Keywords:
metal-organic frameworks (MOFs)
photocatalysis
site-isolated Cu+ centers
transient infrared (TRIR) spectroscopy
UiO-66(Zr)-NH2
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