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Photoreactive Carbon Dioxide Capture by a Zirconium-Nanographene Metal-Organic Framework.
- Source :
-
The journal of physical chemistry letters [J Phys Chem Lett] 2023 May 11; Vol. 14 (18), pp. 4334-4341. Date of Electronic Publication: 2023 May 03. - Publication Year :
- 2023
-
Abstract
- The mechanism of photochemical CO <subscript>2</subscript> reduction to formate by PCN-136, a Zr-based metal-organic framework (MOF) that incorporates light-harvesting nanographene ligands, has been investigated using steady-state and time-resolved spectroscopy and density functional theory (DFT) calculations. The catalysis was found to proceed via a "photoreactive capture" mechanism, where Zr-based nodes serve to capture CO <subscript>2</subscript> in the form of Zr-bicarbonates, while the nanographene ligands have a dual role of absorbing light and storing one-electron equivalents for catalysis. We also find that the process occurs via a "two-for-one" route, where a single photon initiates a cascade of electron/hydrogen atom transfers from the sacrificial donor to the CO <subscript>2</subscript> -bound MOF. The mechanistic findings obtained here illustrate several advantages of MOF-based architectures in molecular photocatalyst engineering and provide insights on ways to achieve high formate selectivity.
Details
- Language :
- English
- ISSN :
- 1948-7185
- Volume :
- 14
- Issue :
- 18
- Database :
- MEDLINE
- Journal :
- The journal of physical chemistry letters
- Publication Type :
- Academic Journal
- Accession number :
- 37133894
- Full Text :
- https://doi.org/10.1021/acs.jpclett.3c00049