Effect of pH-Dependent Homo/Heteronuclear CAHB on Adsorption and Desorption Behaviors of Ionizable Organic Compounds on Carbonaceous Materials

Herein, the adsorption/desorption behaviors of benzoic acid (BA) and phthalic acid (PA) on three functionalized carbon nanotubes (CNTs) at various pH were investigated, and the charge-assisted H-bond (CAHB) was verified by DFT and FTIR analyses to play a key role. The results indicated that the adsorption order of BA and PA on CNTs was different from K(ow) of that at pH 2.0, 4.0, and 7.0 caused by the CAHB interaction. The strength of homonuclear CAHB (≥78.96 kJ·mol(−1)) formed by BA/PA on oxidized CNTs is stronger than that of heteronuclear CAHB formed between BA/PA and amino-functionalized CNTs (≤51.66 kJ·mol(−1)). Compared with the heteronuclear CAHB (Hysteresis index, HI ≥ 1.47), the stronger homonuclear CAHB leads to clearly desorption hysteresis (HI ≥ 3.51). Additionally, the contribution of homonuclear CAHB (≥52.70%) was also greater than that of heteronuclear CAHB (≤45.79%) at pH 7.0. These conclusions were further confirmed by FTIR and DFT calculation, and the crucial evidence of CAHB formation in FTIR was found. The highlight of this work is the identification of the importance and difference of pH-dependent homonuclear/heteronuclear CAHB on the adsorption and desorption behaviors of ionizable organic compounds on carbonaceous materials, which can provide a deeper understanding for the removal of ionizable organic compounds by designed carbonaceous materials.