不同N源无定形TiO2/g-C3N4光催化还原Re(VII)性能

doi:10.15541/jim20200133

无机材料学报 ›› 2020, Vol. 35 ›› Issue (12): 1340-1348.DOI: 10.15541/jim20200133 CSTR: 32189.14.10.15541/jim20200133

所属专题：环境材料论文精选(2020)；【虚拟专辑】放射性污染物去除(2020~2021)

不同N源无定形TiO₂/g-C₃N₄光催化还原Re(VII)性能

王旭聪^1,^2,³(),邓浩³,姜忠义^1,²(),袁立永³()

1. 天津大学化工学院绿色化学化工教育部重点实验室, 天津 300072
2. 天津化学化工协同创新中心, 天津 300072
3. 中国科学院高能物理研究所核能放射化学实验室, 北京 100049

收稿日期:2020-03-16 修回日期:2020-04-20 出版日期:2020-12-20 网络出版日期:2020-06-09
作者简介:王旭聪(1994–), 男, 硕士研究生. E-mail: wangxc@ihep.ac.cn
基金资助:
国家自然科学基金重点项目(21925603);国家自然科学基金重点项目(21836001);国家自然科学基金重点项目(21621004);天津市自然科学基金(18JCYBJC21000)

Photocatalytic Reduction of Re (VII) on Amorphous TiO₂/g-C₃N₄ Derived from Different N Sources

WANG Xucong^1,^2,³(),DENG Hao³,JIANG Zhongyi^1,²(),YUAN Liyong³()

1. Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
2. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China
3. Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

Received:2020-03-16 Revised:2020-04-20 Published:2020-12-20 Online:2020-06-09
About author:WANG Xucong(1994–), male, Master candidate. E-mail: wangxc@ihep.ac.cn
Supported by:
National Natural Science Foundation of China(21925603);National Natural Science Foundation of China(21836001);National Natural Science Foundation of China(21621004);Natural Science Foundation of Tianjin City(18JCYBJC21000)

摘要/Abstract

摘要：

为探究不同N源对无定形TiO₂/g-C₃N₄(TCN)复合材料光催化还原Re(VII)的影响, 通过热分解不同前驱体(尿素Urea、硫脲Thiourea和三聚氰胺Melamine)制备g-C₃N₄, 再分别与无定形TiO₂复合, 制备了三种TCN复合光催化剂。通过不同分析手段对材料进行表征, 并比较了不同TCN复合材料光催化还原去除Re(VII)的活性差异。结果表明, U-TCN(尿素为N源)具有更均匀的表观形貌, 最大的比表面积(474 m²/g), 最优异的光吸收性能, 对Re(VII)的光催化还原效率(90%)明显高于T-TCN(20%)和M-TCN(15%)。通过复合材料的瞬态光电流和电化学阻抗(EIS)分析光催化机理, 证明U-TCN光生电子空穴分离效率最高; 电子顺磁共振波谱(EPR)分析表明U-TCN产生的羟基自由基(?OH)更多, 因此与甲酸反应产生的强还原性?CO₂^-自由基更多, 从而更有利于Re(VII)的还原; 利用同步辐射X射线吸收光谱分析Ti元素价态及配位环境, 表明U-TCN还具有优异的光化学稳定性。本研究揭示了不同N源对所制备TCN复合材料光催化性能的影响, 并发现了一种可用于实际废水中光催化还原去除Tc(VII)的优选材料。

关键词: N源, 无定形TiO₂/g-C₃N₄复合材料, 光催化还原, Re(VII)/Tc(VII)

Abstract:

To clarify the effect of N sources on the photocatalytic reduction of Re (VII) in amorphous TiO₂/g-C₃N₄ (TCN) composites, g-C₃N₄ were prepared via a thermal decomposition of three precursors (Urea, Thiourea and Melamine). Three kinds of TCN composite photocatalysts were then prepared by recombining with amorphous TiO₂ separately. All three photocatalysts were characterized by differnent methods, and their differences in photocatalytic reduction of Re(VII) were compared in detail. The experimental results show that U-TCN using urea as the N source has more uniform appearance, the largest specific surface area (474 m²/g), and the most excellent light absorption performance, leading to its photocatalytic reduction efficiency (90%) for Re (VII) being significantly higher than T-TCN (20%) and M-TCN (15%). Transient photocurrent and electrochemical impedance (EIS) analyses prove that U-TCN exhibits the highest efficiency of photo-generated electron/holes separation. Electron paramagnetic resonance spectroscopy (EPR) analysis shows that U-TCN generates more hydroxyl radicals (?OH), so that there are stronger reducing ?CO₂ radicals produced by the reaction with formic acid, which is more conducive to the reduction of Re (VII). X-ray absorption spectra are employed to analyze the valence state and coordination environment of Ti element, which demonstrates an excellent photochemical stability of U-TCN. The study not only illustrates the effects of N sources on the photocatalytic performance of TCN composites, but also provides a promising photocatalyst for reduction and removal of Tc(VII) from waste water.

Key words: N sources, amorphous TiO₂/g-C₃N₄ composites, photocatalytic reduction, Re(VII)/Tc(VII)

中图分类号:

TQ174

王旭聪, 邓浩, 姜忠义, 袁立永. 不同N源无定形TiO₂/g-C₃N₄光催化还原Re(VII)性能[J]. 无机材料学报, 2020, 35(12): 1340-1348.

WANG Xucong, DENG Hao, JIANG Zhongyi, YUAN Liyong. Photocatalytic Reduction of Re (VII) on Amorphous TiO₂/g-C₃N₄ Derived from Different N Sources[J]. Journal of Inorganic Materials, 2020, 35(12): 1340-1348.

图/表 12

图1 M-CN、T-CN、U-CN、M-TCN、T-TCN和U-TCN样品的XRD图谱

Fig. 1 XRD patterns of M-CN, T-CN, U-CN, M-TCN, T-TCN and U-TCN samples

图2 (a) M-CN、T-CN、U-CN样品和(b)M-TCN、T-TCN和U-TCN样品的FT-IR图谱

Fig. 2 FT-IR spectra of (a) M-CN, T-CN and U-CN samples, and (b) M-TCN, T-TCN and U-TCN samples

图3 (a)U-CN、(b)U-TCN、(c)T-CN、(d)T-TCN、(e)M-CN、(f)M-TCN的SEM照片

Fig. 3 SEM images of (a) U-CN, (b) U-TCN, (c) T-CN, (d) T-TCN, (e) M-CN and (f) M-TCN

图4 M-TCN、T-TCN和U-TCN样品的(a)N2吸附-脱附等温线和(b)孔径分布

Fig. 4 (a) N2 adsorption-desorption isotherms and (b) corresponding pore size distribution curves of M-TCN, T-TCN and U-TCN samples

图5 (a) M-CN、T-CN和U-CN样品和(b) M-TCN、T-TCN和U-TCN样品的UV-Vis光谱

Fig. 5 UV-Vis spectra of (a) M-CN, T-CN and U-CN samples and (b) M-TCN, T-TCN and U-TCN samples

图6 M-TCN、T-TCN、U-TCN和Am-TiO2的PL光谱

Fig. 6 PL spectra of M-TCN, T-TCN, U-TCN and Am-TiO2

图7 (a)U-CN、T-CN、M-CN、Am-TiO2和(b)U-TCN、T-TCN、M-TCN在UV-Vis下还原和去除Re(VII); (c)Langmuir- Hinshelwood动力学方程的线性拟合; (d)U-TCN、(e)T-TCN和(f)M-TCN在UV-Vis光照下降解RhB

Fig. 7 Photocatalytic reduction and removal of Re(VII) using (a) U-CN, T-CN, M-CN, Am-TiO2 and (b) U-TCN, T-TCN and M-TCN composites under UV-Vis irradiation; (c) Linear fitting of Langmuir-Hinshelwood equation; The photodegradation of RhB using 0.4 g?L-1 (d) U-TCN, (e) T-TCN and (f) M-TCN under UV-Vis irradiation

表1 TCN材料光催化还原和去除Re(VII)的动力学参数

Table 1 Kinetic parameters of photocatalytic reduction and removal of Re(VII) using TCN composites

Sample	Re(VII) removed	k/min^-1	R²
U-TCN	90%	0.0788	0.9524
T-TCN	20%	0.0063	0.9861
M-TCN	15%	0.0021	0.7954

图8 U-TCN、T-TCN和M-TCN的(a)瞬态光电流响应和(b)在UV-Vis光照下的EIS曲线

Fig. 8 (a) Transient photocurrent responses and (b) EIS curves of U-TCN, T-TCN and M-TCN composites under UV-Vis irradiation

图9 U-TCN、T-TCN和M-TCN在(a)黑暗条件和(b)紫外可见光照射下EPR谱图

Fig. 9 EPR spectra of U-TCN, T-TCN and M-TCN composites (a) in the dark and (b) under UV-visible light irradiation

图10 Am-TiO2、U-TCN和U-TCN/Re的Ti K-edge XANES分析(a)和EXAFS分析(b)

Fig. 10 (a) Ti K-edge XANES analysis and (b) EXAFS analysis for the Am-TiO2, U-TCN and U-TCN/Re

表2 EXAFS数据分析的拟合参数

Table 2 Fitting parameters from the analysis of EXAFS data

Sample	Bond	N^a	R/nm^b	σ²/nm^{2 c}	R-factor^d
Am-TiO₂	Ti-O	1.2	0.198(3)	3×10^-6
	Ti-O	1.2	0.183(2)	0	0.001
	Ti-Ti	1.0	0.306(2)	6.5×10^-5
U-TCN	Ti-O	1.5	0.192(2)	2×10^-5
	Ti-O	1.0	0.184(3)	0	0.017
	Ti-Ti	1.7	0.312(2)	8.9×10^-5
U-TCN/Re	Ti-O	1.2	0.203(3)	1.0×10^-5
	Ti-O	1.2	0.188(2)	3×10^-6	0.017
	Ti-Ti	1.6	0.314(2)	9.8×10^-5

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不同N源无定形TiO₂/g-C₃N₄光催化还原Re(VII)性能

Photocatalytic Reduction of Re (VII) on Amorphous TiO₂/g-C₃N₄ Derived from Different N Sources

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