铋改性TiO2单晶光催化剂的制备及其完全去除酚类污染物

伴随着人类社会生产生活需要,工业污水中酚类物质的存在极易污染表面水、地下水甚至饮用水.然而,传统污水处理工艺无法对其实现完全去除,更因其稳定的化学结构和难降解特性,对生态系统和人类健康构成了巨大威胁.因此,寻求完全去除水体中酚类污染物是目前环境领域中重要的研究课题之一.二氧化钛因具有优越的物理、化学和光学性能,而被广泛应用于污染物降解研究,然而,传统TiO2光催化剂由于可见光吸收弱和光生电荷高复合率,导致污染物降解效率低,尤其是针对难降解有机污染物如酚类难以实现高效的去除.为此,本文通过引入铋纳米粒子作为TiO2单晶的改性剂,通过充分发挥铋纳米粒子的LSPR效应和TiO2单晶结构的高传导率,不仅有效地拓宽了TiO2的光响应范围(~2.8 eV),而且提高了光生电荷的分离效率,导致其优越的光催化行为.酚类污染物的降解实验表明,所合成的Bi-SCTiO2光催化剂在模拟太阳光照射下,能完全去除水体中的苯酚和对硝基酚,克服了现有以TiO2为基础的光催化剂无法实现酚类污染物完全去除的缺点.更重要的是,当使用环境水如自来水或矿泉水配制苯酚溶液,所制备的Bi-SCTiO2光催化剂仍能实现苯酚的高效降解(>98%);即使采用含有大量有机物质和微生物的长江水所配制的苯酚溶液,在模拟太阳光照射下,Bi-SCTiO2光催化剂对苯酚的降解率仍然高达96%.进一步研究发现,在各种无机离子如Na^+,K^+,Ca^2+,Cl^?,HCO3^?或SO4^2?(0.1 mM)的干扰下,制备的Bi-SCTiO2对苯酚降解率仍然高达98%以上.光催化循环实验表明,所制备的Bi-SCTiO2循环四次后,其对苯酚的降解率几乎保持不变,说明Bi-SCTiO2具有极好的循环稳定性.运用ESR和MS等分析手段,确定了酚类污染物降解的中间体结构、形态和降解路径,再结合Bi-SCTiO2催化剂的光电性能和自由基诱捕实验,提出了酚类污染物完全降解的机理.

Complete removal of phenolic contaminants from bismuth-modified TiO2 single-crystal photocatalysts

Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts. In this study, we designed and synthesized noble metal-free TiO2 photocatalysts by introducing bismuth nano-particles as modifiers of a TiO2 single crystal (Bi-SCTiO2). The Bi-SCTiO2 can make full use of the synergistic effect of a small band overlap and low charge carrier density (Bi) with a high conductivi-ty (single crystal), significantly boosting the separation and migration of the photogenerated charge pairs. Therefore, the Bi-SCTiO2 photocatalyst exhibits a significantly enhanced degradation rate (12 times faster) of 4-nitrophenol than a TiO2 single crystal under simulated sunlight irradiation. Nota-bly, the complete removal of phenolic contaminants is achieved in various water matrices, which not only successfully overcomes the incomplete degradation in many reported photocatalytic sys-tems, but also manifests a significant practical potential for sewage disposal. Therefore, this work presents a new insight in designing and constructing noble metal-free decorated semiconductor single-crystal photocatalysts with excellent activity and cyclability.