High pressure photoreduction of CO₂ inside inorganic and metal organic porous materials

A project funded by the Italian MUR, within the PRIN-PNRR call

People Involved

POLIMI (Politecnico di Milano): Prof. Piero Macchi (unit leader and project principal investigator); Prof. Javier Marti-Rujas; Dr. Anindita Goswani (post doc); Ms. Selene Varliero (PhD Student); Ms. Yidian Wang (PhD student); Mr. Stefano Elli (PhD Student).

UNIFI (University of Florence): Prof. Roberto Bini (unit leader); Prof. Gianni Cardini; Dr. Gianni Pietraperzia; Ms. Selene Berni (PhD Student); Ms. Milo Agati (PhD Student).

CNR (National Research Council – National Institute of optics): Dr. Mario Santoro (unit leader); Dr. Samuele Fanetti; Dr. Demetrio Scelta; Dr. Matteo Ceppatelli

The porous matrices are materials like inorganic zeolites and metal organic frameworks. Both have been already proposed and tested for photoreduction, but without applying compression. On the other hand, it is well known that solids under high pressure may undergo chemical reactions more easily than at ambient conditions, mainly because of the significant reduction of energetic barriers along the reaction paths. Thus, combining porous materials and high pressure is expected to improve the reaction yields making low-cost catalysts more efficient for the photoreduction process. This project deals with alternative and unprecedented solutions for the transformation of CO₂ into valuable chemicals and fuels. The reduction of CO₂ is a necessary step for its removal from the atmosphere or from emissions of exhaust gasses while producing appealing energetic materials. The hypothesis to test in this study is that the photo-chemical reduction of CO₂ can be improved if the reaction occurs in porous matrices subjected to compression.The porous matrices are materials like inorganic zeolites and metal organic frameworks. Both have been already proposed and tested for photoreduction, but without applying compression. On the other hand, it is well known that solids under high pressure may undergo chemical reactions more easily than at ambient conditions, mainly because of the significant reduction of energetic barriers along the reaction paths. The hypothesis will be validated by measuring X-ray diffraction and optical spectroscopy on a series of selected materials, compressed at medium (i.e. kbar regime) or very high pressure (i.e., between 1 and tens of GPa) with simultaneous irradiation in the visible and UV spectral region. The selection of zeolites and MOFs will be assisted by theoretical calculations carried out to predict the high pressure behavior and the improved efficiency under compression.

Results

Publications

Berni, S.; Scelta, D.; Romi, S.; Fanetti, S.; Alabarse, F.; Pagliai M.; Bini, R.
Exploring High-Pressure Polymorphism in Carbonic Acid through Direct Synthesis from Carbon Dioxide Clathrate Hydrate
Angew. Chem. 2024, in the press.
https://onlinelibrary.wiley.com/doi/10.1002/anie.202403953