Mechanistic insights into the selective photocatalytic degradation of dyes over TiO_(2)/ZSM-11

Photocatalytic degradation is a promising way to eliminate dye contaminants.In this work,a series of TiO2/ZSM-11(TZ)nanocomposites were prepared using a facile solid state dispersion method.Methyl orange(MO),methylene blue(MB),and rhodamine B(RhB)were intentionally chosen as target substrates in the photocatalytic degradation reactions.Compared to pristine TiO2,negative effect was observed on MO degradation while promoted kinetics were collected on MB and RhB over TZ composites.Moreover,a much higher photocatalytic rate was interestingly achieved on RhB than MB,which indicated that a new factor has to be included other than the widely accepted electrostatic interaction mechanism to fully understand the selective photodegradation reactions.Systematic characterizations showed that TiO2 and ZSM-11 physically mixed and maintained both the whole framework and local structure without chemical interaction.The different trends observed in surface area and the photo-absorption ability of TZ composites with reaction performance further excluded both as the promotion mechanism.Instead,adsorption energies predicted by molecular dynamics simulations suggested that differences in the adsorption strength played a critical role.This work provided a deep mechanistic understanding of the selective photocatalytic degradation of dyes reactions,which helps to rationally design highly efficient photocatalysts.

Tailoring the microstructure and properties of PES/SPSf loose nanofiltration membranes using SPES as a hydrophilic polymer for the effective removal of dyes via steric hindrance and charge effect

Herein,polyethersulfone(PES)and sulfonated polysulfone(SPSf)blend membranes were prepared with addition of sulfonated polyethersulfone(SPES)as a hydrophilic polymer and adipic acid as a porogen via non-solvent induced phase separation method for effective fractionation of dyes based on the influence of steric hindrance and charge effect.Raman spectroscopy and molecular dynamic simulation modeling confirmed that hydrogen bonds between PES,SPSf,SPES,and adipic acid were crucial to membrane formation and spatial arrangement.Further addition of hydrophilic SPES resulted in a membrane with reduced pore size and molecular weight cut-off as well as amplified negative charge and pure water permeance.During separation,the blend membranes exhibited higher rejection rates for nine types of small molecular weight(269.3–800 Da)dyes than for neutral polyethylene glycol molecules(200–1000 Da).This was attributed to the size effect and the synergistic effect between steric hindrance and charge repulsion.Notably,the synergistic impact decreased with dye molecular weight,while greater membrane negative charge enhanced small molecular dye rejection.Ideal operational stability and anti-fouling performance were best observed in M2(PES/SPSf/SPES,3.1 wt%).Summarily,this study demonstrates that SPES with–SO3‒functional groups can be applied to control the microstructure and separation of membranes.