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

Xin Zheng, Matthew C. Drummer, Haiying He, Thomas M. Rayder, Jens Niklas, Nicholas P. Weingartz, Igor L. Bolotin, Varun Singh, Boris V. Kramar, Lin X. Chen, Joseph T. Hupp, Oleg G. Poluektov, Omar K. Farha, Peter Zapol, Ksenija D. Glusac*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


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” mechanism, where Zr-based nodes serve to capture CO2 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 CO2-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.

Original languageEnglish (US)
Pages (from-to)4334-4341
Number of pages8
JournalJournal of Physical Chemistry Letters
Issue number18
StatePublished - May 11 2023

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry


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