Doping copper ions in a metal-organic framework (UiO-66-NH2): Location effect examined by ultrafast spectroscopy

We constructed two types of copper-doped metal-organic framework (MOF), i.e ., Cu@UiO- 66-NH 2 and Cu-UiO-66-NH 2 . In the former, Cu 2+ ions are impregnated in the pore space of the amine-functionalized, Zr-based UiO-66-NH 2 ; while in the latter, Cu 2+ ions are in-corporated to form a bimetal-center MOF, with Zr 4+ being partially replaced by Cu 2+ in the Zr−O oxo-clusters. Ultrafast spectroscopy revealed that the photoinduced relaxation kinetics associated with the ligand-to-cluster charge-transfer state is promoted for both Cu-doped MOFs relative to undoped one, but in a sequence of Cu-UiO-66-NH 2 >Cu@UiO-66-NH 2 >UiO-66-NH 2 . Such a sequence turned to be in line with the trend observed in the visible-light photocatalytic hydrogen evolution activity tests on the three MOFs. These findings highlighted the subtle effect of copper-doping location in this Zr-based MOF system, further suggesting that rational engineering of the specific metal-doping location in alike MOF systems to promote the photoinduced charge separation and hence suppress the detrimental charge recombination therein is beneficial for achieving improved performances in MOF-based photocatalysis.