Mechanochemical vs Wet Approach for Directing CO₂ Capture toward Various Carbonate and Bicarbonate Networks

The distinct research areas related to CO₂ capture and mechanochemistry are both highly attractive in the context of green chemistry. However, merger of these two areas, i.e., mechanochemical CO₂ capture, is still in an early stage of development. Here, the application of biguanidine as an active species for CO₂ capture is investigated using both solution-based and liquid-assisted mechanochemical approaches, which lead to a variety of biguanidinium carbonate and bicarbonate hydrogen-bonded networks. We demonstrate that in solution, the formation of the carbonate vs bicarbonate networks can be directed by the organic solvent, while, remarkably, in the liquid-assisted mechanochemical synthesis employing the same solvents as additives, the selectivity in network formation is inversed. In general, our findings support the view of mechanochemistry not only as a sustainable alternative but rather as a complementary strategy to solution-based synthesis.