Dynamic structural twist in metal–organic frameworks enhances solar overall water splitting

• Published in: Nature chemistry 2024-10, Vol.16 (10), p.1638-1646
• Main Authors: Sun, Kang, Huang, Yan, Sun, Fusai, Wang, Qingyu, Zhou, Yujie, Wang, Jingxue, Zhang, Qun, Zheng, Xusheng, Fan, Fengtao, Luo, Yi, Jiang, Jun, Jiang, Hai-Long
• Format: Article
• Language: English
• Subjects: 639/638/298/921; 639/638/77/887; 639/638/77/890; 639/925/357/404; Analytical Chemistry; Biochemistry; Catalysts; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Crystallography; Excitation; Hydrogen production; Inorganic Chemistry; Metal-organic frameworks; Organic Chemistry; Photocatalysis; Photocatalysts; Photochemicals; Photoexcitation; Physical Chemistry; Quantum efficiency; Recombination; Splitting; Water splitting; Zinc
• ISSN: 1755-4330; 1755-4349; 1755-4349
• DOI: 10.1038/s41557-024-01599-6

Photocatalytic overall water splitting holds great promise for solar-to-hydrogen conversion. Maintaining charge separation is a major challenge but is key to unlocking this potential. Here we discovered a metal–organic framework (MOF) that shows suppressed charge recombination. This MOF features electronically insulated Zn 2+ nodes and two chemically equivalent, yet crystallographically independent, linkers. These linkers behave as an electron donor–acceptor pair with non-overlapping band edges. Upon photoexcitation, the MOF undergoes a dynamic excited-state structural twist, inducing orbital rearrangements that forbid radiative relaxation and thereby promote a long-lived charge-separated state. As a result, the MOF achieves visible-light photocatalytic overall water splitting, in the presence of co-catalysts, with an apparent quantum efficiency of 3.09 ± 0.32% at 365 nm and shows little activity loss in 100 h of consecutive runs. Furthermore, the dynamic excited-state structural twist is also successfully extended to other photocatalysts. This strategy for suppressing charge recombination will be applicable to diverse photochemical processes beyond overall water splitting. Solar water splitting holds great promise for hydrogen production but is significantly hindered by rapid recombination of photogenerated charges. Now a metal–organic framework photocatalyst has been shown to undergo, upon photoexcitation, a dynamic excited-state structural twist that greatly suppresses charge recombination to enable efficient photocatalytic overall water splitting.