水凝胶负载的纳米银/氮化碳光催化剂的制备及性能研究

doi:10.15541/jim20210535

无机材料学报 ›› 2022, Vol. 37 ›› Issue (7): 731-740.DOI: 10.15541/jim20210535 CSTR: 32189.14.10.15541/jim20210535

所属专题：【能源环境】光催化(202312)；【信息功能】MAX层状材料、MXene及其他二维材料(202409)

水凝胶负载的纳米银/氮化碳光催化剂的制备及性能研究

王晓俊¹(), 许文², 刘润路¹, 潘辉¹^,³(), 朱申敏¹()

1.上海交通大学金属基复合材料国家重点实验室, 上海 200240
2.上海绘兰材料科技有限公司, 上海 201507
3.上海交通大学化学化工学院, 上海 200240

收稿日期:2021-08-27 修回日期:2022-01-24 出版日期:2022-07-20 网络出版日期:2022-02-21
通讯作者: 朱申敏, 教授. E-mail: smzhu@sjtu.edu.cn;
潘辉, 博士. E-mail: panhui115@hotmail.com
作者简介:王晓俊(1999-), 男, 学士. E-mail: chunyu@sjtu.edu.cn
基金资助:
国家自然科学基金(51672173)

Preparation and Properties of Ag@C₃N₄ Photocatalyst Supported by Hydrogel

WANG Xiaojun¹(), XU Wen², LIU Runlu¹, PAN Hui¹^,³(), ZHU Shenmin¹()

1. State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China
2. Shanghai Huilan Material Technology Co., LTD, Shanghai 201507, China
3. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2021-08-27 Revised:2022-01-24 Published:2022-07-20 Online:2022-02-21
Contact: ZHU Shenmin, professor. E-mail: smzhu@sjtu.edu.cn;
PAN Hui, PhD. E-mail: panhui115@hotmail.com
About author:WANG Xiaojun (1999-), male, Bachelor. E-mail: chunyu@sjtu.edu.cn
Supported by:
National Natural Science Foundation of China(51672173)

摘要/Abstract

摘要：

石墨相氮化碳(g-C₃N₄)具有独特的二维平面结构和半导体能带结构, 广泛应用于光催化。但其又存在光生电子空穴对复合过快、可见光利用效率低、在水中分散性差等问题, 阻碍了其实际应用。本研究以海藻酸钠制备的水凝胶为基体, 通过与负载银纳米颗粒(AgNPs)的g-C₃N₄复合, 提升光生电子-空穴的分离效率, 同时解决催化剂在水中的分散性问题, 改善其光催化性能。首先, 采用热聚合法合成g-C₃N₄, 结合超声的高能量使其剥离成纳米片; 然后采用溶液法在g-C₃N₄表面原位生成银纳米颗粒, 制备得到负载银纳米颗粒的g-C₃N₄(Ag@C₃N₄); 最后以海藻酸钠(SA)为前驱体通过钙离子交联的方法得到负载有Ag@C₃N₄的水凝胶(SA/Ag@C₃N₄)。通过不同手段表征SA/Ag@C₃N₄的形貌、微观结构和相组成; 以甲基橙为模型物, SA/Ag@C₃N₄的光催化降解速率是Ag@C₃N₄的2.5倍。通过光致发光谱、时间分辨光致发光谱、电子顺磁共振波谱等表征手段对材料的催化机理进行探究。结果显示, 体系中银纳米颗粒表面等离子体共振效应与海藻酸钠水凝胶的多孔结构及传质通道发挥协同效应, 促进了光催化性能的提升。

关键词: 氮化碳, 银纳米颗粒, 海藻酸钠, 水凝胶, 光催化

Abstract:

Graphitic carbon nitride (g-C₃N₄) is widely used in the field of photocatalysis due to its unique two-dimensional planar structure and suitable energy band structure. However, it has some disadvantages such as fast recombination of the electron-hole, low visible-light utilization efficiency and poor dispersion in water, which hinder its application. In this study, the hydrogel prepared by sodium alginate was used as matrix to improve the dispersion of Ag@C₃N₄ composite in water, and at the same time enhanced the separation efficiency of photoelectron-holes pairs, thus improving its photocatalytic performance. Firstly, g-C₃N₄ was synthesized by thermal polymerization and then exfoliated into nanosheets by ultrasound. Then, Ag nanoparticles were deposited in situ on the surface of g-C₃N₄ by solution method to prepare Ag@C₃N₄. Finally, hydrogel loaded with Ag@C₃N₄ (SA/Ag@C₃N₄) was obtained by using calcium ion as crosslinker and sodium alginate (SA) as precursor. The morphology, microstructure and phase composition of the as-prepared photocatalyst were characterized. The as-prepared SA/Ag@C₃N₄ exhibited a 1.5 times higher photocatalytic degradation rate of methyl orange than that of Ag@C₃N₄. The catalytic mechanism was investigated by photoluminescence spectrum, time resolved photoluminescence spectrum and electron paramagnetic resonance spectrum. The results showed that the surface plasmon resonance effect of silver nanoparticles together with the porous structure and mass transfer channel of sodium alginate hydrogel plays a synergistic role in the enhancement of photocatalytic performance.

Key words: carbon nitride, silver nanoparticles, sodium alginate, hydrogel, photocatalysis

中图分类号:

TQ426

王晓俊, 许文, 刘润路, 潘辉, 朱申敏. 水凝胶负载的纳米银/氮化碳光催化剂的制备及性能研究[J]. 无机材料学报, 2022, 37(7): 731-740.

WANG Xiaojun, XU Wen, LIU Runlu, PAN Hui, ZHU Shenmin. Preparation and Properties of Ag@C₃N₄ Photocatalyst Supported by Hydrogel[J]. Journal of Inorganic Materials, 2022, 37(7): 731-740.

图/表 13

图1 g-C3N4 (a), Ag@C3N4 (b), SA (c)和SA/AgC3N4 (d)的宏观形貌

Fig. 1 Macro morphologies of g-C3N4 (a), Ag@C3N4 (b), SA (c), and SA/Ag@C3N4 (d)

图2 C3N4 (a), Ag@C3N4 (b), SA/Ag@C3N4 (c, d)的SEM照片; Ag@C3N4的TEM (e)和HRTEM(f)照片

Fig. 2 SEM images of C3N4 (a), Ag@C3N4 (b) and SA/Ag@C3N4 (c, d), TEM (e) and HRTEM (f) images of Ag@C3N4

图3 C3N4, Ag@C3N4, SA, SA/Ag@C3N4的FT-IR谱图

Fig. 3 FT-IR spectra of C3N4, Ag@C3N4, SA, and SA/Ag@C3N4 Colorful figures are available on the website

图4 C3N4, Ag@C3N4, SA, SA/Ag@C3N4的XRD图谱(a); SA/Ag@C3N4的XRD放大图谱(b)

Fig. 4 XRD patterns of C3N4, Ag@C3N4, SA and SA/Ag@C3N4 (a), and magnified XRD patterns of SA/Ag@C3N4(b) Colorful figures are available on the website

图5 C3N4, Ag@C3N4, SA/Ag@C3N4的氮气吸附-脱附曲线(a)和孔径分布曲线(b)

Fig. 5 N2 adsorption-desorption isotherms (a) and pore size distribution curves (b) of C3N4, Ag@C3N4 and SA/Ag@C3N4 Colorful figures are available on the website

图6 Ag@C3N4的SEM照片(a), Ag@C3N4的EDX元素分布图((b) C, (c) N, (d) Ag)

Fig. 6 SEM image (a) and EDX element mappings of Ag@C3N4 sample ((b) C, (c) N, (d) Ag)

图7 C3N4 (a, b), Ag@C3N4 (c, d), SA/Ag@C3N4 (e~g)的X射线光电子能谱

Fig. 7 XPS spectra of C3N4 (a, b), Ag@C3N4 (c, d) and SA/Ag@C3N4 (e-g) (a, c, e) C1s; (b, d, f) N1s; (g) Ag3d

图8 C3N4, Ag@C3N4, SA, SA/Ag@C3N4对甲基橙的光降解曲线 (a)、光降解速率 (b)以及SA/Ag@C3N4的循环稳定性 (c)

Fig. 8 Methyl orange degradation curves (a), degradation rates (b) of C3N4, Ag@C3N4, SA, and SA/Ag@C3N4, and cyclic stability(c) of SA/Ag@C3N4 Colorful figures are available on the website

图9 C3N4, Ag@C3N4, SA/Ag@C3N4的PL光谱(a)和TRPL光谱(b)

Fig. 9 PL (a) and TRPL (b) spectra of C3N4, Ag@C3N4 and SA/Ag@C3N4 Colorful figures are available on the website

图10 C3N4, Ag@C3N4, SA, SA/Ag@C3N4的(a)紫外-可见漫反射光谱和(b) (αhν)0.5随hν的变化曲线

Fig. 10 (a) UV-Vis diffuse reflection spectra and (b) (αhν)0.5 vs hν curves of C3N4, Ag@C3N4, SA and SA/Ag@C3N4 Colorful figures are available on the website

图11 (a, b) C3N4, (c, d) Ag@C3N4, (e, f) SA/Ag@C3N4的EPR曲线

Fig. 11 EPR spectra of C3N4 (a, b), Ag@C3N4 (c, d) and SA/Ag@C3N4 (e, f) during detecting ·OH (a, c, e) and ·O2- (b, d, f) Colorful figures are available on the website

图12 C3N4, Ag@C3N4的光电流曲线(a)和EIS曲线(b)

Fig. 12 Transient photocurrent curves (a) and EIS curves (b) of C3N4 and Ag@C3N4 Colorful figures are available on the website

图13 SA/Ag@C3N4的结构示意图和催化机理

Fig. 13 Schematic diagram and catalytic mechanism of SA/Ag@C3N4

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水凝胶负载的纳米银/氮化碳光催化剂的制备及性能研究

Preparation and Properties of Ag@C₃N₄ Photocatalyst Supported by Hydrogel

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[15]	洪佳辉, 马冉, 仵云超, 文涛, 艾玥洁. MOFs自牺牲模板法制备CoN_x/g-C₃N₄纳米材料用作高效光催化还原U(VI)[J]. 无机材料学报, 2022, 37(7): 741-749.

水凝胶负载的纳米银/氮化碳光催化剂的制备及性能研究

Preparation and Properties of Ag@C3N4 Photocatalyst Supported by Hydrogel

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Preparation and Properties of Ag@C₃N₄ Photocatalyst Supported by Hydrogel