Tailoring molecular permeability of vertically-ordered mesoporous silica-nanochannel films on graphene for selectively enhanced determination of dihydroxybenzene isomers in environmental water samples

Herein we demonstrate a simple and rapid electrochemical method for selectively enhanced determination of catechol (CC) or hydroquinone (HQ) isomers in environmental water samples by tailoring the molecular permeability of vertically-ordered mesoporous silica-nanochannel films on electrochemically reduced graphene oxide (VMSF/ErGO). Such VMSF/ErGO composite film was fabricated on the gold electrode (AuE) surface using electrochemically assisted self-assembly approach. The as-prepared electrodes with surfactant micelles (SM) template inside silica nanochannels, designed as SM/VMSF/ErGO/AuE, possess hydrophobic hydrocarbon cores and show preferential response to CC via hydrophobic effect. After removing SM from silica nanochannels, the obtained VMSF/ErGO/AuE displays more sensitive response to HQ, which is due to the hydrogen bond effect between the silanol groups of silica walls and HQ. Given the potential-resolved and high electrocatalytic ability of ErGO, and molecular permeability and anti-fouling ability of VMSF, these two present sensors could detect CC and HQ in lake water with a low limit of detection (18 nM for CC and 16 nM for HQ), and a high sensitivity (0.33 μA/μM for CC and 0.37 μA/μM for HQ), without complicated sample pretreatment . Moreover, the proposed sensors provide a convenient, rapid and economic way for direct analysis of environmental water samples, exhibiting excellent long-term stability.