Doping [Ru(bpy)3]2+ into metal-organic framework to facilitate the separation and reuse of noble-metal photosensitizer during CO2 photoreduction

Abstract

It is desirable to develop highly efficient and sustainable catalytic systems for CO2 photoreduction using efficient heterogeneous photosensitizers (PSs); however, this remains a great challenge. In this study, we doped [Ru(bpy)3]2+ into UiO-metal-organic frameworks (MOFs) to facilitate the separation and reuse of noble metal PS. By simply adjusting the loading amount, a series of heterogeneous photoactive MOFs, namely, UiO-Ru-1, UiO-Ru-2, and UiO-Ru-3, were constructed to act as heterogeneous PSs to drive the efficient CO2 photoreduction under visible-light irradiation. Remarkably, UiO-Ru-2 exhibited the best photosensitizing ability among the prepared MOFs in sensitizing the iron quarterpyridine catalyst (C-1), and the CO yield reached as high as 171 mmol/g with ca. 100% selectivity, which is a record value among all the MOF-based photocatalysts. This photoactive MOF can be recycled and reused three times without any obvious activity loss, signifying its good photochemical stability. Experimental investigations confirmed that the strong visible absorption, long-lived excited state, appropriate redox potential, good photocatalytic stability, and excellent collaboration with C-1 were attributable to the superior catalytic activity. This work highlights an avenue for constructing heterogeneous PSs with excellent recyclability using MOF as the platform for efficient CO2 reduction.