Room temperature design of Ce(iv)-MOFs: from photocatalytic HER and OER to overall water splitting under simulated sunlight irradiation

The development of MOF-based efficient and reusable catalysts for hydrogen production under simulated sunlight irradiation, especially through overall water splitting, remains challenging. This is mainly due to either the inappropriate optical features or poor chemical stability of the given MOFs. Room temperature synthesis (RTS) of tetravalent MOFs is a promising strategy to design robust MOFs and their related (nano)composites. By employing these mild conditions, herein, we report for the first time that RTS leads to the efficient formation of highly redox active Ce(iv)-MOFs that are inaccessible at elevated temperatures. Consequently, not only highly crystalline Ce-UiO-66-NH(2) is synthesized, but also many other derivatives and topologies (8 and 6-connected phases) without compromise in space-time yield. Their photocatalytic HER and OER activities under simulated sunlight irradiation are in good agreement with their energy level band diagrams: Ce-UiO-66-NH(2) and Ce-UiO-66-NO(2) are the most active photocatalysts for the HER and OER, respectively, with a higher activity than other metal-based UiO-type MOFs. Combining Ce-UiO-66-NH(2) with supported Pt NPs results finally in one of the most active and reusable photocatalysts for overall water splitting into H(2) and O(2) under simulated sunlight irradiation, due to its efficient photoinduced charge separation evidenced by laser flash photolysis and photoluminescence spectroscopies.