三维大孔g-C3N4吸附和光催化还原U(VI)性能研究

doi:10.15541/jim20190336

无机材料学报 ›› 2020, Vol. 35 ›› Issue (3): 359-366.DOI: 10.15541/jim20190336

所属专题： 2020年环境材料论文精选(一)放射性元素去除；【虚拟专辑】放射性污染物去除(2020~2021)

三维大孔g-C₃N₄吸附和光催化还原U(VI)性能研究

蒋丽¹,高慧慧¹,曹茹雅^1,²,张守伟¹(),李家星²()

^1. 济南大学物理科学与技术学院, 济南 250022
^2. 中国科学院等离子体物理研究所, 合肥 230031

收稿日期:2019-07-05 修回日期:2019-08-07 出版日期:2020-03-20 网络出版日期:2019-09-04
作者简介:蒋丽(1997-), 女, 学士. E-mail: ax459684525@163.com
基金资助:
国家自然科学基金(21707043);国家自然科学基金(21876178);国家自然科学基金(21677146);山东省自然科学基金(ZR2017BEE005)

Construction of Novel Three Dimensionally Macroporous g-C₃N₄ for Efficient Adsorption/Photocatalytic Reduction of U(VI)

JIANG Li¹,GAO Huihui¹,CAO Ruya^1,²,ZHANG Shouwei¹(),LI Jiaxing²()

^1. School of Physics and Technology, University of Jinan, Jinan 250022, China
^2. Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031, China

Received:2019-07-05 Revised:2019-08-07 Published:2020-03-20 Online:2019-09-04
About author:JIANG Li, female, Bachelor. E-mail: ax459684525@163.com
Supported by:
National Natural Science Foundation of China(21707043);National Natural Science Foundation of China(21876178);National Natural Science Foundation of China(21677146);Natural Science Foundation of Shandong Province(ZR2017BEE005)

摘要/Abstract

摘要：

将易溶的U(VI)还原为微溶的U(IV)是治理放射性铀污染的有效方法。本研究以SiO₂纳米球作为硬模板, 通过热聚合-刻蚀制备具有连续贯通的三维大孔g-C₃N₄光催化剂, 用于吸附-光催化还原U(VI)。材料表征结果显示: 三维大孔g-C₃N₄比表面积显著增加, 对可见光的吸收明显增强; 同时具有三维有序大孔结构, 并呈规则的紧密堆积结构, 孔壁完整多孔, 整个结构具有良好的三维连通性。吸附实验表明: 三维大孔g-C₃N₄对U(VI)最大吸附容量可达~30.5 mg/g, 该过程更符合Langmuir吸附模型, 与块体g-C₃N₄相比吸附容量提高了~1.83倍。光催化还原实验表明: 三维大孔g-C₃N₄具有高的光催化活性和良好的稳定性, 其还原反应速率常数为~0.0142 min ^-1, 是块体g-C₃N₄(~0.0024 min ^-1)的~5.9倍。鉴于三维大孔g-C₃N₄具有较优异的吸附-催化还原性能, 该材料有望应用于放射性废水中U(VI)的快速高效清除。

关键词: 三维大孔g-C₃N₄, U(VI), 吸附, 光催化还原

Abstract:

Reduction of soluble U(VI) to insoluble U(IV) oxide is an effective approach to control uranium contamination. Three-dimensional (3D) macroporous g-C₃N₄ photocatalyst with interconnected porous was prepared by thermal polymerization and template etching using self-assembly of SiO₂ nanosphere as the template. The material was then applied to adsorption-photocatalytic reduction of U(VI). Characterization results showed that the 3D macroporous g-C₃N₄ photocatalyst presented a well-defined interconnected macroporous architecture and numerous nanopores existed on the well-defined macroporous skeleton. 3D macroporous g-C₃N₄ also had a significant increase in specific surface area which was beneficial to the absorption of visible light. Adsorption results showed that the maximum adsorption capacity of U(VI) on 3D macroporous g-C₃N₄ was ~30.5 mg/g, which was more than ~1.83 times higher than that of bulk g-C₃N₄. The adsorption isotherm matched well with the Langumuir equation. Photocatalytic reduction experiments showed that the 3D macroporous g-C₃N₄ had high photocatalytic activity and good stability with the reduction rate constant of 0.0142 min ^-1, which was ~4.9 times higher than bulk g-C₃N₄ (~0.0024 min ^-1). As the sorption-photocatalytic performance of the sample is excellent, 3D macroporous g-C₃N₄ is a high efficient visible-light-responsive photocatalyst for the removal of U(VI) from radioactive wastewater.

Key words: 3D macroporous g-C₃N₄, U(VI), adsorption, photocatalytic reduction

中图分类号:

TQ174

蒋丽, 高慧慧, 曹茹雅, 张守伟, 李家星. 三维大孔g-C₃N₄吸附和光催化还原U(VI)性能研究[J]. 无机材料学报, 2020, 35(3): 359-366.

JIANG Li, GAO Huihui, CAO Ruya, ZHANG Shouwei, LI Jiaxing. Construction of Novel Three Dimensionally Macroporous g-C₃N₄ for Efficient Adsorption/Photocatalytic Reduction of U(VI)[J]. Journal of Inorganic Materials, 2020, 35(3): 359-366.

图/表 7

图1 块体g-C3N4和三维大孔g-C3N4的XRD图谱(a)和FT-IR光谱(b)

Fig. 1 XRD patterns (a) and FT-IR spectra (b) of the bulk g-C3N4 and 3D macroporous g-C3N4

图2 块体g-C3N4和三维大孔g-C3N4的UV-Vis DRS谱图(a)和比表面积图(b)

Fig. 2 UV-Vis diffuse reflectance spectra (a) and surface areas (b) of the bulk g-C3N4 and 3D macroporous g-C3N4

图3 块体g-C3N4(a, b)和三维大孔g-C3N4(c, d)的SEM和TEM照片

Fig. 3 SEM and TEM images of the bulk g-C3N4 (a, b) and 3D macroporous g-C3N4 (c, d)

图4 块体g-C3N4和三维大孔g-C3N4吸附U(VI)的动力学曲线(a)和吸附等温线(b)

Fig. 4 (a) Adsorption kinetics and (b) adsorption isotherms for U(VI) on bulk g-C3N4 and 3D macropoous g-C3N4 pH=5.0±0.1, T=293 K, m/V=0.5 g/L The insert in (a) is the pseudo-second-order kinetic plots

表1 准一级和准二级动力学模型拟合参数

Table 1 Fitting parameters of pseudo-first-order and pseudo-second-order kinetic models

Sample	Pseudo-first-ordermodel		Pseudo-second-ordermodel
Sample	k₁/min^-1	R²	k₂/(g∙mg^-1∙min^-1)	R²
Bulk g-C₃N₄	0.0761	0.983	0.0493	0.999
3D macroporous g-C₃N₄	0.1087	0.992	0.0721	0.999

图5 块体g-C3N4和三维大孔g-C3N4的可见光催化还原U(VI)性能图(a)和还原反应速率(b), 三维大孔g-C3N4的循环实验(c)和光催化反应前后U元素的XPS图谱(d)

Fig. 5 (a) Dark adsorption and photocatalytic reduction of U(VI) and (b) the rate constant with bulk g-C3N4 and 3D macroporous g-C3N4, (c) cycling runs of 3D macroporous g-C3N4 for the photocatalytic reduction of U(VI) and (d) U4f specta of 3D macroporous g-C3N4 before and after U(VI) photoreduction

图6 块体g-C3N4和三维大孔g-C3N4的(a)光电流响应图谱和(b)电化学阻抗谱

Fig. 6 (a) Transient photocurrent responses and (b) electrochemical impedance spectra of bulk g-C3N4 and 3D macroporous g-C3N4

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三维大孔g-C₃N₄吸附和光催化还原U(VI)性能研究

Construction of Novel Three Dimensionally Macroporous g-C₃N₄ for Efficient Adsorption/Photocatalytic Reduction of U(VI)

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