Utilisation of CO2 as “Structure Modifier” of Inorganic Solids

Francesconi, M. Grazia; Bennett, Matthew J; Benoit, David; Dobson, Ian

Abstract

Utilisation of CO2 as a chemical reagent is challenging, due to the molecule’s inherent chemical stability. However, CO2 reacts promptly at high temperature (~1000 C) with alkaline-earth oxides to form carbonates and such reactions are used towards capture and re-utilisation. In this work, this concept is extended and CO2 is utilised as a reagent to modify the crystal structure of mixed-metal inorganic solids. Modification of the crystal structure is a “tool” used by materials scientists to tailor the physical property of solids. CO2 gas was reacted with several isostructural mixed-metal oxides Sr2CuO3, Sr1.8Ba0.2CuO3 and Ba2PdO3. These oxides are carefully selected to show anion vacancies in their crystal structure, to act as host sites for CO2 molecules, leading to the formation of carbonate anions, (CO3)2. The corresponding oxide carbonates were formed successfully and the favourable formation of SrCO3 as secondary phase was minimised via an innovative, yet simple synthetic procedure involving alternating of CO2 and air. We also derived a simple model to predict the kinetics of the reactions for the cuprates, using first-principles density functional theory and assimilating the reaction to a gas–surface process.

Citation

Francesconi, M. G., Bennett, M. J., Benoit, D., & Dobson, I. (2022). Utilisation of CO2 as “Structure Modifier” of Inorganic Solids. Chemistry: a European journal, 28(6), Article e202103608. https://doi.org/10.1002/chem.202103608

• Journal Article Type: Article
• Acceptance Date: Dec 8, 2021
• Online Publication Date: Dec 21, 2021
• Publication Date: Jan 27, 2022
• Deposit Date: Feb 2, 2022
• Publicly Available Date: Dec 22, 2022
• Journal: Chemistry - A European Journal
• Print ISSN: 0947-6539
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 28
• Issue: 6
• Article Number: e202103608
• DOI: https://doi.org/10.1002/chem.202103608
• Keywords: Carbon dioxide fixation; Intercalation; Main groups elements; Perovskite phases; Transition metals
• Public URL: https://hull-repository.worktribe.com/output/3884577