Solvothermal synthesis of carbonate-type layered double hydroxide monolayer nanosheets: Solvent selection based on characteristic parameter matching criterion.

Monolayer nanosheets of CO32--type layered double hydroxides (LDHs) have many special applications, but their fabrication is challenging. Herein, Co2Al-CO3 and Co2Fe-CO3 LDH nanosheets were synthesized via a solvothermal method. 31 solvents with different characteristic parameters, including the surface free energy (γ) and solubility (δ) parameters were chosen, to explore the correlation between the formation of monolayer LDHs (ML-LDHs) and the characteristic parameters of solvents. The results reveal that when the solvents used have the characteristic parameters matching to those of the LDHs, CO32--type ML-LDHs with a thickness of ca. 1 nm can be obtained. The mixed-solvent strategy can provide the effective solvents for the synthesis of ML-LDHs. The dispersions of CO32--type ML-LDHs can be stable for at least six months without obvious precipitation. In addition, it is demonstrated that the δ parameters of LDHs can be calculated from the γ parameters via the molar volume-free γ-δ equations developed previously. Furthermore, a new parameter called "surface free energy distance" is introduced, which can be used for screening effective solvents for the synthesis of ML-LDHs. To the best of our knowledge, this is the first time to investigate the applicable of the characteristic parameter matching principle for the bottom-up synthesis of ML-LDHs. This work deepens the understanding on the feature of CO32--type LDHs and provides a solvent selection strategy for the synthesis of CO32--type ML-LDHs.