Abnormal Enhanced Free Ions of Ionic Liquids Confined in Carbon Nanochannels

Revealing the structure and behavior of confined ionic liquids (ILs) is essential for their applications in green chemical processes. Here, we explore the electroconductivity (σ) and ionic correlation of imidazole ILs confined in graphene nanochannels via joint molecular dynamics simulation and theoretical analysis. The ideal and actual σ of ILs are first calculated, showing a growing tendency and up to the bulk value as the nanochannel size ranges from 1 to 10 nm. To account for the ionic correlation, the ionicity was determined by the ratio of the actual to ideal σ, reflecting the average fraction of free ions in the confined ILs. Amazingly, the ionicity of all three ILs shows an abnormal changing tendency, which first increases and reaches the maximum at 2 nm and then decreases to the bulk value. The conformational analysis, pair dissociating energy, and residence time are further obtained, proving that the abnormal enhanced ionicity should be attributed to the structure reconstruction of ILs near the graphene wall. The analytical model of ionicity herein can guide the rational design of efficient IL-based nanoporous electrodes and solid catalysts.