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

• Published in: SusMat (Online) Vol. 2; no. 6; pp. 708 - 719
• Main Authors: Wang, Yang, Shi, Litong, Hu, Haijun, Qian, Bingzhi, Hou, Wei, Li, Hui, Liu, Xue, Liu, Daliang, Wu, Shuyao, Huang, Hongwei, Song, Xi‐Ming, Zhang, Yu, Ma, Tianyi
• Format: Journal Article
• Language: English
• Published: Chengdu John Wiley & Sons, Inc 01-12-2022; Wiley
• Subjects: Acids; Aqueous solutions; Catalysts; Chloride; Chloride ions; Chlorine; Decomposition; Hydrogen; Hydrogen evolution; Hydrogen reduction; Impurities; Ligands; Metals; Nanomaterials; Nanotechnology; Photocatalysis; photocatalytic hydrogen evolution; Radiation; Seawater; seawater splitting; Semiconductor materials; Spectrum analysis; sub‐nanometric material; trinuclear metal‐oxo complex; Vapor phases; Beijing China; China
• ISSN: 2692-4552; 2766-8479; 2692-4552
• DOI: 10.1002/sus2.89

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 μmol 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 metal‐oxo 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‐metal‐free catalysts and low‐cost candidates for traditional semiconductor materials in enhancing photocatalytic efficiency and performing chlorine evolution from seawater splitting.
Two homogeneous photocatalytic systems based on trinuclear metal‐oxo complexes have been first constructed and experimentally confirmed to be competent for seawater hydrogen evolution up to 48 h. The chloride ions in the seawater act as the hole catcher and move into the gas phase in the stable form of chlorine. The combination of two metal‐oxo cluaters hinders the self‐reduction process that occurs when the metal‐oxo clusters consume photogenerated electrons, thereby not only improving the hydrogen production performance, but also ensuring the stability of the photocatalysts.