Mechanistic study of pressure and temperature dependent structural changes in reactive formation of silicon carbonate

Abstract

The discovery of the silicon carbonate through chemical reaction between porous SiO₂ and gaseous CO₂ addressed a long-standing question regarding whether the reaction between CO₂ and SiO₂ is possible. However, the detailed atomic structure of silicon carbonate and associated reaction mechanism are still largely unknown. We explore structure changes of silicon carbonate with pressure and temperature based on systematic ab initio molecular dynamics simulations. Our simulations suggest that the reaction proceeds at the surface of the porous SiO₂. Increasing number of CO₂ molecules can take part in the reaction by increasing either the pressure or temperature. The final product of the reaction exhibits amorphous structures, where most C atoms and Si atoms are 3-fold and 6-fold coordinated, respectively. The fraction of differently coordinated C (Si) atoms is pressure dependent, and as a result, the structure of the final product is pressure dependent as well. When releasing the pressure, part of the reaction product decomposes into CO₂ molecules and SiO₂ tetrahedrons. However more than 50% of C atoms are still in 3-fold coordination, implying that stable silicon carbonate may be obtained via repeated annealing under high pressure. The mechanism underlying this chemical reaction is predicted with two possible reaction pathways identified. Moreover, the reaction transition curve is obtained from the extensive simulation, which can be useful to guide the synthesis of silicon carbonate from the reaction between SiO₂ and CO₂.