The Role of Water in Carbon Dioxide Adsorption in Porphyrinic Metal‐Organic Frameworks

Author:

Baumgartner Bettina1,Prins P. Tim1,Louwen Jaap N.1,Monai Matteo1,Weckhuysen Bert M.1ORCID

Affiliation:

1. Debye Institute for Nanomaterials Science and Institute for Sustainable and Circular Chemistry, Department of Chemistry Utrecht University Universiteitsweg 99 3584 CG Utrecht The Netherlands

Abstract

AbstractCapturing and converting CO2 through artificial photosynthesis using photoactive, porous materials is a promising approach for addressing increasing CO2 concentrations. Porphyrinic Zr‐based metal‐organic frameworks (MOFs) are of particular interest as they incorporate a photosensitizer in the porous structure. Herein, the initial step of the artificial photosynthesis is studied: CO2 sorption and activation in the presence of water. A combined vibrational and visible spectroscopic approach was used to monitor the adsorption of CO2 into PCN‐222 and PCN‐223 MOFs, and the photophysical changes of the porphyrinic linker as a function of water concentration. A shift in CO2 sorption site and bending of the porphyrin macrocycle in response to humidity was observed, and CO2/H2O competition experiments revealed that the exchange of CO2 with H2O is pore‐size dependent. Therefore, humidity and pore‐size can be used to tune CO2 sorption, CO2 capacity, and light harvesting in porphyrinic MOFs, which are key factors for CO2 photoreduction.

Funder

Ministry of Education, Culture, Sports, Science and Technology

Austrian Science Fund

Nederlandse Organisatie voor Wetenschappelijk Onderzoek

Publisher

Wiley

Subject

Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Catalysis

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