Surface-Degenerate Semiconductor Photocatalysis for Efficient Water Splitting without Sacrificial Agents via a Reticular Chemistry Approach |
| |
Authors: | Li Shiuan Ng Dr. Tharishinny Raja Mogan Jinn-Kye Lee Dr. Haitao Li Dr. Chi-Lik Ken Lee Prof. Hiang Kwee Lee |
| |
Affiliation: | 1. Division of Chemistry and Biological Chemistry, School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore;2. School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002 PR China;3. Institute of Sustainability for Chemicals, Energy and Environment (ISCE2), The Agency for Science, Technology and Research (A*STAR), Jurong Island, Singapore, 627833 Singapore |
| |
Abstract: | The production of green hydrogen through photocatalytic water splitting is crucial for a sustainable hydrogen economy and chemical manufacturing. However, current approaches suffer from slow hydrogen production (<70 μmol ⋅ gcat−1 ⋅ h−1) due to the sluggish four-electrons oxygen evolution reaction (OER) and limited catalyst activity. Herein, we achieve efficient photocatalytic water splitting by exploiting a multifunctional interface between a nano-photocatalyst and metal–organic framework (MOF) layer. The functional interface plays two critical roles: (1) enriching electron density directly on photocatalyst surface to promote catalytic activity, and (2) delocalizing photogenerated holes into MOF to enhance OER. Our photocatalytic ensemble boosts hydrogen evolution by ≈100-fold over pristine photocatalyst and concurrently produces oxygen at ideal stoichiometric ratio, even without using sacrificial agents. Notably, this unique design attains superior hydrogen production (519 μmol ⋅ gcat−1 ⋅ h−1) and apparent quantum efficiency up to 13-fold and 8-fold better than emerging photocatalytic designs utilizing hole scavengers. Comprehensive investigations underscore the vital role of the interfacial design in generating high-energy photoelectrons on surface-degenerate photocatalyst to thermodynamically drive hydrogen evolution, while leveraging the nanoporous MOF scaffold as an effective photohole sink to enhance OER. Our interfacial approach creates vast opportunities for designing next-generation, multifunctional photocatalytic ensembles using reticular chemistry with diverse energy and environmental applications. |
| |
Keywords: | Metal–Organic Framework Nanoparticles Photocatalysis Semiconductor Water Splitting |
|
|