Decipher the molecular descriptors and mechanisms controlling sulfonamide adsorption onto mesoporous carbon: Density functional theory calculation and partial least-squares path modeling

Mesoporous carbons (MCs) exhibit excellent removal efficiencies to various organic chemicals. However, how the properties of chemicals influence the adsorption mechanisms and further determine their adsorption onto MCs are poorly understood. We investigated the adsorption of 22 sulfonamides (SAs) onto four MCs, and further uncovered the major molecular descriptors and adsorption mechanisms influencing the adsorption by density functional theory (DFT) and partial least-squares path modeling (PLS-PM). The results revealed that the excess molar refraction (E), McGowan's molar volume (V), energy of the highest occupied molecular orbital (EHOMO), hardness (H), and most positive net charge on carbon atom (Qc+) were identified as the indirect factors affecting the distribution coefficient (logKD), by influencing the BE(π-π), BE(H), and logKow. BE(π-π) and logKow displayed significant direct impacts on logKD (p < 0.05), while BE(H) showed insignificant direct influences on logKD (p > 0.05). The PLS-PM results indicate the main driving forces for SAs adsorption including π-π interactions, hydrophobic effects, and hydrogen bonding. This study provides a new perspective on revealing the adsorption mechanisms, and the identified factors can be used to develop the quantitative model to further predict the adsorption of SAs onto MCs.