Year: 2023
Type: article
Abstract: The mechanism of photochemical CO2 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” mecha-nism, where Zr-based nodes serve to capture CO2 in the form of Zr-bicarbonates, while the nanographene ligands have a dual role to absorb light and to store one-electron equivalents needed 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 CO2-bound MOF. The mechanistic findings obtained here illustrate several advantages of MOF-based architectures in the molecular photocatalyst engineering and provide insights on ways to achieve high formate selectivity.
Language: English
Field: Energy
Domain: Physical Sciences
SDG: Climate action
Open Access status: green
Funders: National Science Foundation, U.S. Department of Energy, Northwestern University, Office of Science, Materials Research Science and Engineering Center, Harvard University, Division of Materials Research, Division of Electrical, Communications and Cyber Systems, Basic Energy Sciences, Argonne National Laboratory
Awards: G102163711, G107546177, G1169090945, NNCI: Soft Hybrid Nanotechnology Experimental (SHyNE) Resource, G1286251239, G1313983767, G1329306526, G1664757510, SPATIO-TEMPORAL DYNAMICS OF CO2 CAPTURE BY SORBENTS: MULTIMODAL, IN-SITU AND OPERANDO MEASUREMENTS, INTRAMOLECULAR ELECTRON TRANSFER RATES, G222768804, G2233802770, G2287611682, G262962599, G3010471893, G3075337988, G316399430, G3454132534, G3589692066, G3954585026, G4120964173, G426311843, G4285583887, G4289625387, G4574467239, G461010968, MRSEC: Center for Multifunctional Materials, FUNDAMENTAL STUDIES OF LIGHT-INDUCED CHARGE TRANSFER, ENERGY TRANSFER, AND ENERGY CONVERSION WITH SUPRAMOLECULAR SYSTEMS, G4912152698, G4958141111, G498139845, G513797252, G5218300437, G5387317844, G5648016710, G6540817556, G6848031779, G6918803902, G7304483037, FUNDAMENTAL STUDIES OF LIGHT-INDUCED CHARGE TRANSFER, ENERGY TRANSFER, AND ENERGY CONVERSION WITH SUPRAMOLECULAR SYSTEMS, G7583137537, G801469781, G969889393, G993149817
OpenAlex ID: W4367835085