Bioinspired Self‐Assembly of Metalloporphyrins and Polyelectrolytes into Hierarchical Supramolecular Nanostructures for Enhanced Photocatalytic H2 Production in Water

• Published in: Angewandte Chemie International Edition Vol. 63; no. 8; pp. e202315599 - n/a
• Main Authors: Tang, Qingxuan, Han, Yifei, Chen, Lingxuan, Qi, Qiaoyan, Yu, Junlai, Yu, Shang‐Bo, Yang, Bo, Wang, Hao‐Yang, Zhang, Jiangshan, Xie, Song‐Hai, Tian, Feng, Xie, Zhenhua, Jiang, Hanqiu, Ke, Yubin, Yang, Guanyu, Li, Zhan‐Ting, Tian, Jia
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 19-02-2024
• Edition: International ed. in English
• Subjects: Active sites; Biomimetics; Catalysts; Chromophores; Copper; Electron transfer; Hydrogen; Hydrogen production; Photocatalysis; Photosynthesis; Polyelectrolytes; Polymers; Polypeptides; Porphyrinoids; Porphyrins; Self-Assembly; Porphyrinoids Polymers Self-assembly Photocatalysis Hydrogen
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202315599

Polypeptides, as natural polyelectrolytes, are assembled into tailored proteins to integrate chromophores and catalytic sites for photosynthesis. Mimicking nature to create the water‐soluble nanoassemblies from synthetic polyelectrolytes and photocatalytic molecular species for artificial photosynthesis is still rare. Here, we report the enhancement of the full‐spectrum solar‐light‐driven H2 production within a supramolecular system built by the co‐assembly of anionic metalloporphyrins with cationic polyelectrolytes in water. This supramolecular photocatalytic system achieves a H2 production rate of 793 and 685 μmol h−1 g−1 over 24 h with a combination of Mg or Zn porphyrin as photosensitizers and Cu porphyrin as a catalyst, which is more than 23 times higher than that of free molecular controls. With a photosensitizer to catalyst ratio of 10000 : 1, the highest H2 production rate of >51,700 μmol h−1 g−1 with a turnover number (TON) of >1,290 per molecular catalyst was achieved over 24 h irradiation. The hierarchical self‐assembly not only enhances photostability through forming ordered stackings of the metalloporphyrins but also facilitates both energy and electron transfer from antenna molecules to catalysts, and therefore promotes the photocatalysis. This study provides structural and mechanistic insights into the self‐assembly enhanced photostability and catalytic performance of supramolecular photocatalytic systems.
Inspired by the assembly of bilins in phycobilisome through the assistance of protein scaffold, hierarchical supramolecular nanostructures have been constructed by the co‐assembly of artificial polyelectrolyte scaffolds and metalloporphyrins in water. This supramolecular assembly system resulted in a photocatalytic H2 production rate of>51700 μmol h−1g−1 and a turnover number of 1299 per molecular catalyst over 24 h.