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The photoreduction deposition method is employed to fabricate a family of silver nanoparticle (Ag NP)-modified polyoxometalate-based metal–organic framework (NENU-5) photocatalysts, named Ag/NENU-5. The title photocatalysts, Ag/NENU-5, can be used for the photocatalytic reduction of CO2and are observed to efficiently reduce CO2into CO, in which the highest reduction rate is 22.28 μmol g–1h–1, 3 times greater than that of NENU-5. Photocatalytic reduction performances of CO2have been extremely improved after the incorporation of Ag NPs as the cocatalyst. The enhancement of the photocatalytic reduction of CO2has been attributed to the synergistic effects of Ag NPs and NENU-5, inhibiting the charge recombination during the photocatalytic process and increasing the reaction active sites. Furthermore, the influence of Ag NPs on the photocatalytic activity has also been investigated. The experimental results clearly reveal that the size of Ag NPs could exert a main effect on the photocatalytic activity, and the reasonable size of Ag NPs is able to enhance the photocatalytic reduction activity toward CO2significantly.

Metal–organic frameworks constructed from Zr usually possess excellent chemical and physical stability. Therefore, they have become attractive platforms in various fields. In this work, two families of hybrid materials based on ZrSQU have been designed and synthesized, named Im@ZrSQU and Cu@ZrSQU, respectively. Im@ZrSQU was prepared through the impregnation method and employed for proton conduction. Im@ZrSQU exhibited terrific proton conduction performance in an anhydrous environment, with the highest proton conduction value of 3.6 × 10–2S cm–1at 110 °C. In addition, Cu@ZrSQU was synthesized via the photoinduction method for the photoreduction of CO2, which successfully promoted the conversion of CO2into CO and achieved the CO generation rate of up to 12.4 μmol g–1h–1. The photocatalytic performance of Cu@ZrSQU is derived from the synergistic effect of Cu NPs and ZrSQU. Based on an in-depth study and discussion toward ZrSQU, we provide a versatile platform with applications in the field of proton conduction and photocatalysis, which will guide researchers in their further studies.