Photoreactive Carbon Dioxide Capture by a Zirconium-Nanographene Metal-Organic Framework.

Autor: Zheng X; Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States., Drummer MC; Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States.; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States., He H; Department of Physics and Astronomy, Valparaiso University, Valparaiso, Indiana 46383, United States., Rayder TM; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States., Niklas J; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States., Weingartz NP; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States., Bolotin IL; Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States., Singh V; Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States.; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States., Kramar BV; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States., Chen LX; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States., Hupp JT; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States., Poluektov OG; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States., Farha OK; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States., Zapol P; Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States., Glusac KD; Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States.; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.
Jazyk: angličtina
Zdroj: 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.
DOI: 10.1021/acs.jpclett.3c00049
Abstrakt: The mechanism of photochemical CO 2 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 2 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 2 -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.
Databáze: MEDLINE
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