铋改性TiO2单晶光催化剂的制备及其完全去除酚类污染物

doi:10.1016/S1872-2067(20)63668-3

催化学报 ›› 2021, Vol. 42 ›› Issue (2): 347-355.DOI: 10.1016/S1872-2067(20)63668-3

铋改性TiO₂单晶光催化剂的制备及其完全去除酚类污染物

汤文杰^a, 陈娟荣^b, 尹正亮^a, 盛维琛^a^,^*(), 林逢建^a, 许辉^b, 曹顺生^a^,^#()

^a江苏大学材料学院高分子研究院, 江苏镇江212013
^b江苏大学环境与安全工程学院能源研究所, 江苏镇江212013

收稿日期:2020-04-16 接受日期:2020-05-29 出版日期:2021-02-18 发布日期:2021-01-21
通讯作者: 盛维琛,曹顺生
基金资助:
国家自然科学基金(21876069);国家自然科学基金(21707054);江苏省“六大人才”高峰计划(XCL-018)

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

Wenjie Tang^a, Juanrong Chen^b, Zhengliang Yin^a, Weichen Sheng^a^,^*(), Fengjian Lin^a, Hui Xu^b, Shunsheng Cao^a^,^#()

^aResearch School of Polymer Materials, School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China
^bSchool of the Environment and Safety Engineering, Institute for Energy Research, Jiangsu University, Zhenjiang 212013, Jiangsu, China

Received:2020-04-16 Accepted:2020-05-29 Online:2021-02-18 Published:2021-01-21
Contact: Weichen Sheng,Shunsheng Cao
About author:^#E-mail: sscao@ujs.edu.cn
^*Tel: +86-511-88780911; E-mail: shengweichen@ujs.edu.cn;
Supported by:
National Natural Science Foundation of China(21876069);National Natural Science Foundation of China(21707054);Six Talent Peaks Project in Jiangsu(XCL-018)

摘要/Abstract

摘要：

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⁺, Ca²⁺, 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.

关键词: 铋改性, 二氧化钛单晶, 酚类污染物, 完全去除, 水体, 降解机理, 光催化作用

Abstract:

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 nanoparticles 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 conductivity (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. Notably, the complete removal of phenolic contaminants is achieved in various water matrices, which not only successfully overcomes the incomplete degradation in many reported photocatalytic systems, 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.

Key words: Bi modification, TiO₂ single crystal, Phenolic pollutants, Complete removal, Water matrix, Degradation mechanism, Photocatalysis

汤文杰, 陈娟荣, 尹正亮, 盛维琛, 林逢建, 许辉, 曹顺生. 铋改性TiO₂单晶光催化剂的制备及其完全去除酚类污染物[J]. 催化学报, 2021, 42(2): 347-355.

Wenjie Tang, Juanrong Chen, Zhengliang Yin, Weichen Sheng, Fengjian Lin, Hui Xu, Shunsheng Cao. Complete removal of phenolic contaminants from bismuth-modified TiO₂ single-crystal photocatalysts[J]. Chinese Journal of Catalysis, 2021, 42(2): 347-355.

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https://www.cjcatal.com/CN/Y2021/V42/I2/347

图/表 9

Fig. 1. (a) Schematic of the preparation of Bi-SCTiO2 nanorods; SEM (b), TEM (c), HRTEM (d), and SAED (e) images of Bi-SCTiO2; STEM mapping of the Bi-SCTiO2 photocatalyst ((g) Ti; (h) O; (i) Bi).

Fig. 2. (a) XRD patterns of SCTiO2 and Bi-SCTiO2; XPS profiles in the full-scale (b), Ti 2p (c), O 1s (d), and C 1s (e) regions of the SCTiO2 and Bi-SCTiO2 samples; (f) the Bi 4f region for the Bi-SCTiO2 sample.

Fig. 3. Photocatalytic degradation (a) and corresponding fitting curves (b) of 4-NP; (c) Effect of the initial concentration of 4-NP on the performance of Bi-SCTiO2; photocatalytic degradation (d) and corresponding fitting curves (e) of phenol; (f) Effect of the initial concentration of phenol on the performance of Bi-SCTiO2.

Fig. 4. The effects of pH (a), metal cations (b), Cl- (c), HCO3- (d), SO42- (e), and water matrix (f) on the degradation of phenol (initial concentration of phenol = 10 mg/L) under simulated sunlight irradiation.

Fig. 5. (a) Photocatalytic performance of Bi-SCTiO2 for degrading 4-NP; ESR spectra of DMPO-?OH (b), DMPO-?O2- (c), and TEMPO-h+ (d) over SCTiO2 and Bi-SCTiO2.

Fig. 6. UV-vis spectra (a) and corresponding bandgap (b) of the SCTiO2 and Bi-SCTiO2; (c) transient photocurrent responses; (d) EIS of SCTiO2 and Bi-SCTiO2.

Fig. 7. Mechanism of photocatalytic degradation.

Fig. 8. Possible degradation pathway of 4-NP (a) and phenol (b).

Fig. 9. Recycling performance of Bi-SCTiO2 for degrading phenol under simulated sunlight irradiation.

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铋改性TiO₂单晶光催化剂的制备及其完全去除酚类污染物

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

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