Abstract
Metal-organic frameworks (MOFs) with customizable components can photo-reduce CO2 into various products; however, tuning the distribution of these products through modification engineering remains challenging. In this study, we propose a novel bottom-up surfactant-assisted preorganization strategy to simultaneously disrupt inner Van der Waals forces and induce Ti cation vacancies in the well-known NH2-MIL-125 MOF. The resulting Ti-deficient NH2-MIL-125 nanosheets, featuring unpaired electrons on O atoms and residual Ti sites, not only significantly enhance photo-generated charge migration but also facilitate the further protonation of CO* to CHO* during CO2 photoreduction. Unlike NH2-MIL-125, which predominantly converts CO2 to CO, the Ti-deficient NH2-MIL-125 nanosheets achieve an impressive selectivity of 95.7 % for CH4 production, with an electron consumption rate of 51.0 mol·g−1·h−1 for the first time. This approach of creating metal-cation vacancies to synergistically modulate charge separation dynamics and catalytic reaction kinetics offers a new pathway to refine the activity and selectivity of multifaceted competitive catalytic reactions.
Original language | English |
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Article number | 124938 |
Journal | Applied Catalysis B: Environmental |
Volume | 365 |
DOIs | |
State | Published - 15 May 2025 |
Keywords
- CO reduction
- Cation vacancy
- Metal-organic frameworks
- Unpaired electrons