Binary trinuclear metal-oxo sub-nanomaterials for photocatalytic hydrogen and chlorine production from seawater

Owing to the need for regenerant and self-reduction problem, the hydrogen performance of sub-nano-sized trinuclear iron-oxo complexes is still far from satisfied with affordability and practicality. Herein, two binary photocatalytic systems based on trinuclear metal-oxo complexes have been first constructed and experimentally confirmed to be competent for seawater hydrogen evolution (715.4 and 271.9 mu mol of hydrogen can be found, respectively, after 48 h). Notably, chloride ions act as the hole catcher and move into the gas phase in the stable form of chlorine. Similar to heterogeneous structures, homogeneous systems not only enhance the hydrogen performance while ensuring the stability of metaloxo complexes, but also shorten the consumption of photogenerated carriers by dissolved impurities in the seawater. This new attempt of building pluralistic sub-nanometric systems may offer novel design strategies with noble-metalfree catalysts and low-cost candidates for traditional semiconductor materials in enhancing photocatalytic efficiency and performing chlorine evolution from seawater splitting.