SnS2-Ag/g-C3N4三相复合材料的合成及其光催化性能

刘成宝; 唐飞; 马恬; 陈丰; 钱君超; 许小静; 孟宪荣; 陈志刚

doi:10.13801/j.cnki.fhclxb.20220117.003

SnS₂-Ag/g-C₃N₄三相复合材料的合成及其光催化性能

doi: 10.13801/j.cnki.fhclxb.20220117.003

刘成宝^{1, 2, 3, ,},
唐飞^{1, 2},
马恬^{1, 2},
陈丰^{1, 2, 3},
钱君超^{1, 2, 3},
许小静⁴,
孟宪荣⁵,
陈志刚^{1, 2, 3}

1.
苏州科技大学　江苏省环境功能材料重点实验室，苏州 215009
2.
苏州科技大学　材料科学与工程学院，苏州 215009
3.
苏州科技大学　江苏水处理技术与材料协同创新中心，苏州 215009
4.
江苏省陶瓷研究所有限公司，宜兴 214221
5.
苏州市环境科学研究所，苏州 215007

基金项目: 江苏省自然科学基金(BK20180103；BK20180971)；苏州市科技发展计划项目(民生科技—关键技术应用研究)(SS202036)；江苏省研究生实践创新计划(SJCX20_1107)

详细信息

通讯作者:
刘成宝，博士，副教授，研究方向为环境功能材料　E-mail: Lcb@mail.usts.edu.cn

中图分类号: TB333
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- 被引次数: 0
出版历程
- 收稿日期: 2021-10-27
- 修回日期: 2022-01-03
- 录用日期: 2022-01-07
- 网络出版日期: 2022-01-18
- 刊出日期: 2022-12-01

Preparation and photocatalytic properties of SnS₂-Ag/g-C₃N₄ composites

LIU Chengbao^{1, 2, 3
, ,},
TANG Fei^{1, 2},
MA Tian^{1, 2},
CHEN Feng^{1, 2, 3},
QIAN Junchao^{1, 2, 3},
XU Xiaojing⁴,
MENG Xianrong⁵,
CHEN Zhigang^{1, 2, 3}

1.
Jiangsu Key Laboratory for Environment Functional Materials, Suzhou University of Science and Technology, Suzhou 215009, China
2.
School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou 215009, China
3.
Jiangsu Collaborative Innovation Center of Technology and Material for Water Treatment, Suzhou University of Science and Technology, Suzhou 215009, China
4.
Jiangsu Province Ceramics Research Institute CO., LTD., Yixing 214221, China
5.
Suzhou Institute of Environmental Science, Suzhou 215007, China

摘要

摘要: 为解决单相光催化材料结构和性能上的缺陷，通过二次煅烧法获得二维石墨相氮化碳g-C₃N₄，通过光沉积法获得Ag/g-C₃N₄，选择SnS₂与Ag/g-C₃N₄通过简单的超声和蒸发溶剂的方法制备了三相复合材料SnS₂-Ag/g-C₃N₄，成功构建了n-n型异质结，并对材料的微观形貌、相结构、光响应能力和孔隙结构等进行了详尽表征。结果表明：材料依然保留了片层状结构并构建了浪花状形貌，各相结晶度较高且界面构建良好，形成了类似三明治结构的2D-0D-2D形貌，复合材料较单相材料具有更高的比表面积和更强的可见光响应性能。当SnS₂的含量为10wt%时，所合成SnS₂-Ag/g-C₃N₄复合材料对罗丹明B的光催化降解效率达到最高的95.6%，降解速率最快且为g-C₃N₄的3.5倍，经4次循环后材料的光催化效率仍然保持在85.3%以上。
- 石墨相氮化碳 /
- 硫化锡 /
- 银 /
- 复合材料 /
- 光催化 /
- 降解
Abstract: In order to solve the defects in the structure and performance of single-phase photocatalytic materials, the 2D graphitic carbon nitride (g-C₃N₄) was synthesized by secondary calcining, and Ag/g-C₃N₄ was prepared via photodeposition method. SnS₂-Ag/g-C₃N₄ with n-n type heterojunction structure was prepared through simple ultrasonic and solvent evaporation methods. The microstructure, phase structure, light response ability and pore structure of the materials were characterized. The results showed that the lamellar structure and the spray shape coexist in the composite. The 2D-0D-2D morphology similar to sandwich structure is formed. The composite has high crystallinity and well-constructed interface, which give it a higher specific surface area and stronger visible light response performance. When the mass fraction of SnS₂ is 10wt%, the photocatalytic degradation efficiency of the SnS₂-Ag/g-C₃N₄ composite is up to 95.6%, and the degradation rate is 3.5 times as that of g-C₃N₄. After 4 cycles, the photocatalytic efficiency remained above 85.3%.
- graphitic carbon nitride /
- SnS₂ /
- Ag /
- composite /
- photocatalysis /
- degradation

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图 1 不同分散剂用量合成的SnS₂(a) 和不同质量分数的SnS₂-Ag/g-C₃N₄(b) 的XRD图谱

Figure 1. XRD patterns of SnS₂ synthesized with different dispersant dosages (a) and SnS₂-Ag/g-C₃N₄ synthesized with different proportions (b)

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图 2 0.3SnS₂(a)、0.6SnS₂(b) 和0.9SnS₂(c) 的SEM图像

Figure 2. SEM images of 0.3SnS₂(a), 0.6SnS₂(b) and 0.9SnS₂(c)

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图 3 5wt% (a)、10wt% (b)、15wt% (c) SnS₂-Ag/g-C₃N₄的SEM图像

Figure 3. SEM image of 5wt% (a), 10wt% (b), 15wt% (c) SnS₂-Ag/g-C₃N₄

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图 4 SnS₂-Ag/g-C₃N₄复合光催化材料的HRTEM图像 (a)、面扫图谱 (b) 和C、N、Ag、Sn和S元素 ((c)~(g))

Figure 4. HRTEM image (a), mapping spectrum (b) of SnS₂-Ag/g-C₃N₄ composite photocatalytic material, elements of C, N, Ag, Sn and S, respectively ((c)-(g))

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图 5 g-C₃N₄和10wt%SnS₂-Ag/g-C₃N₄的N₂吸附-脱附等温线 (a) 及对应的孔径分布 (b)

Figure 5. N₂ adsorption-desorption isotherms (a) of g-C₃N₄ and 10wt%SnS₂-Ag/g-C₃N₄ and their corresponding pore size distributions (b)

V—Pore volume; D—Pore diameter

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图 6 g-C₃N₄、Ag/g-C₃N₄和SnS₂-Ag/g-C₃N₄催化剂材料的荧光光谱图

Figure 6. Fluorescence spectra of g-C₃N₄, Ag/g-C₃N₄ and SnS₂-Ag/g-C₃N₄ catalyst materials

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图 7 SnS₂-Ag/g-C₃N₄的X射线光电子能谱(XPS)光谱图(a)和C1s(b)、N1s(c)、Sn3d(d)、S2p(e)和Ag3d(f)的高分辨率XPS光谱

Figure 7. X-ray photoelectron spectroscopy (XPS) spectra(a) of SnS₂-Ag/g-C₃N₄ and high-resolution XPS spectra of C1s(b), N1s(c), Sn3d(d), S2p(e) and Ag3d(f)

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图 8 SnS₂、g-C₃N₄、Ag/g-C₃N₄、SnS₂-Ag/g-C₃N₄的UV-Vis漫反射光谱 (a) 及其对应的带隙宽度图 (b)

Figure 8. UV–Vis diffuse reflectance spectras of SnS₂, g-C₃N₄, Ag/g-C₃N₄, SnS₂-Ag/g-C₃N₄(a) and band gap width diagram of catalysts, respectively (b)

α—Absorption coefficient; hv—Optical energy

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图 9 不同SnS₂含量的SnS₂-Ag/g-C₃N₄对RhB的光催化降解速率 (a) 和动力学图 (b)；(c) 不同pH条件下催化剂的降解效率； (d) 催化材料的稳定性

Figure 9. Photocatalytic degradation rate (a) and kinetic (b) diagram of RhB by SnS₂-Ag/g-C₃N₄ with different SnS₂ content; (c) Degradation efficiency of catalyst under different pH conditions; (d) Stability of catalytic materials

k—Reaction rate constant; C—Concentration; C₀—Original concentration

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图 10 (a) 不同清除剂加入后SnS₂-Ag/g-C₃N₄降解罗丹明B(RhB)的效率；(b) 催化剂材料的价带谱

Figure 10. (a) SnS₂-Ag/g-C₃N₄ degradation efficiency of Rhodamine B (RhB) after adding different scavengers; (b) Valence band of the catalyst material

EDTA-2Na—C₁₀H₁₄N₂Na₂O₈; t-BuOH—Tertiary butyl alcohol; BQ—Benzoquinone

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图 11 SnS₂-Ag/g-C₃N₄光催化材料的机制示意图

Figure 11. Schematic diagram of the mechanism of SnS₂-Ag/g-C₃N₄

CB—Conduction band; VB—Valence band; E—Potential

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表 1 层状SnS₂的配比

Table 1. Ratio of layered SnS₂

Sample	PEG-6000/g	Sn/mmol	S/mmol
0.3SnS₂	0.3	1	2
0.6SnS₂	0.6	1	2
0.9SnS₂	0.9	1	2
Note: PEG—Polyethylene glycol.

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表 2 SnS₂-Ag/石墨相氮化碳(g-C₃N₄)样品名及其成分配比

Table 2. Sample name of SnS₂-Ag/graphite phase carbon nitride (g-C₃N₄) and composition ratio

Sample	0.3SnS₂/wt%	Ag/wt%
5%SnS₂-Ag/g-C₃N₄	5	5
10%SnS₂-Ag/g-C₃N₄	10
15%SnS₂-Ag/g-C₃N₄	15

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