SiO2增强自敏性氮化碳微球可见光降解盐酸四环素的研究

doi:10.15541/jim20240009

无机材料学报 ›› 2024, Vol. 39 ›› Issue (7): 787-792.DOI: 10.15541/jim20240009

SiO₂增强自敏性氮化碳微球可见光降解盐酸四环素的研究

曹青青(), 陈翔宇, 吴健豪, 王筱卓, 王乙炫, 王禹涵, 李春颜, 茹菲, 李兰, 陈智()

中国计量大学材料化学学院, 杭州 310018

收稿日期:2024-01-04 修回日期:2024-03-03 出版日期:2024-03-08 网络出版日期:2024-03-08
通讯作者: 陈智, 博士, 副教授. E-mail: zchen@cjlu.edu.cn
作者简介:曹青青(2000-), 女, 硕士研究生. E-mail: 2024225003@qq.com
基金资助:
国家重点研发计划(2023YFF0612600);浙江省尖兵领雁项目(2023C02038);宁波市重大科技任务攻关项目(2022Z178);中建股份科技重点研发项目(CSCEC-2021-Z-5);国家级大学生创新创业训练计划(202210356009);浙江省高分子材料表界面重点实验室开放基金(SISPM-2022-03)

Visible-light Photodegradation of Tetracycline Hydrochloride on Self-sensitive Carbon-nitride Microspheres Enhanced by SiO₂

CAO Qingqing(), CHEN Xiangyu, WU Jianhao, WANG Xiaozhuo, WANG Yixuan, WANG Yuhan, LI Chunyan, RU Fei, LI Lan, CHEN Zhi()

College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China

Received:2024-01-04 Revised:2024-03-03 Published:2024-03-08 Online:2024-03-08
Contact: CHEN Zhi, PhD, associate professor. E-mail: zchen@cjlu.edu.cn
About author:CAO Qingqing (2000-), female, Master candidate. E-mail: 2024225003@qq.com
Supported by:
National Key Research and Development Program of China(2023YFF0612600);Key Research and Development Program of Zhejiang Province(2023C02038);Key Research and Development Program of Ningbo(2022Z178);China Construction Technology Research and Development Project(CSCEC-2021-Z-5);National Training Programs of Innovation and Entrepreneurship for Undergraduates(202210356009);Open Research Fund Program of Key Laboratory of Surface & Interface Science of Polymer Materials of Zhejiang Province(SISPM-2022-03)

摘要/Abstract

摘要：

光催化技术在水中新型污染物的治理中应用广泛。自敏性氮化碳(SSCN)是一种新型非金属光催化剂, 其表面的自敏性高分子可以有效地拓宽可见光吸收范围, 但该材料存在严重的团聚现象, 抑制了其光催化活性和稳定性。SiO₂的分散性好, 被广泛用作载体构建复合结构应用于光催化领域。本研究首先用Stöber法制备了SiO₂微球, 随后利用水热法原位合成了SiO₂/SSCN复合材料。采用多种表征手段分析样品的物相结构、微观形貌、光电性能。制备的复合材料在光催化降解水中盐酸四环素中表现出增强的降解活性, 其活性与SiO₂加入量密切相关, 当SiO₂与SSCN的质量比为0.04 ∶ 1时, 复合材料的光催化活性和稳定性最佳, 光照60 min可降解42%的盐酸四环素, 经5次循环后其光催化降解效率仍然能够维持约38%。引入的SiO₂为SSCN提供了分散位点, 改善了SSCN较为严重的团聚现象, 使SSCN表面的1,3,5-三嗪基低聚物(TBO)快速分解后达到表面活性位点暴露的最佳含量, 提升了SSCN对可见光的利用率, 促进了光生电荷的分离效率, 从而有效地提升了SSCN的光催化活性及稳定性。本研究为提高催化剂的光催化活性和稳定性及治理新型污染物提供了一个新思路。

关键词: 自敏性氮化碳, 二氧化硅, 光催化, 盐酸四环素, 活性增强

Abstract:

Photocatalysis is widely employed to treat emerging pollutants in water, due to its well-organized attributes. Self-sensitive carbon nitride (SSCN) represents a novel class of non-metallic photocatalyst that has garnered significant attention for its distinctive properties in contrast with traditional graphitic carbon nitride (g-C₃N₄). However, their visible-light photodegradation effect remained still to be enhanced. Here, SiO₂ microspheres were initially synthesized by the Stöber method, followed by the preparation of SiO₂/SSCN composites through an in-situ hydrothermal process. Their microstructure, phase structure, and photoelectric properties were systematically investigated using a combination of characterization techniques. It is discovered that the SiO₂ within the composites effectively disperses in the SSCN. The obtained composite material was then applied to photocatalytic degradation of antibiotic pollutants in water, exhibiting enhanced degradation activity, which was closely correlated with the quantity of SiO₂. At mass ratio of SiO₂ to SSCN of 0.04 : 1, the composite achieved optimal photocatalytic activity and demonstrated good stability. After irradiation for 60 min, 42% of tetracycline hydrochloride was degraded, and the photocatalytic degradation efficiency remained at 38% after 5 cycles. Furthermore, incorporation of the SiO₂ component offers supplementary sites for the dispersion of SSCN, mitigating serious agglomeration phenomenon of SSCN. This facilitates the rapid decomposition of 1,3,5-triazine oligomers (TBO) on the surface of SSCN under light irradiation, and the optimizing content of TBO on surface active sites. Consequently, utilization efficiency of visible light on SSCN is significantly improved, and a higher separation rate of photogenerated electron-hole pairs is simultaneously observed. These attributes culminate in significantly improved photocatalytic activity for the degradation of tetracycline hydrochloride on SSCN under visible light irradiation. Above advantages may position the as-synthesized SiO₂ dispersed SSCN as prospective candidate for practical application. Therefore, this research offers a novel route for enhancing the photocatalytic activity and stability of catalysts.

Key words: self-sensitive carbon nitride, silicon dioxide, photocatalysis, tetracycline hydrochloride, enhanced activity

中图分类号:

X52
TQ174

曹青青, 陈翔宇, 吴健豪, 王筱卓, 王乙炫, 王禹涵, 李春颜, 茹菲, 李兰, 陈智. SiO₂增强自敏性氮化碳微球可见光降解盐酸四环素的研究[J]. 无机材料学报, 2024, 39(7): 787-792.

CAO Qingqing, CHEN Xiangyu, WU Jianhao, WANG Xiaozhuo, WANG Yixuan, WANG Yuhan, LI Chunyan, RU Fei, LI Lan, CHEN Zhi. Visible-light Photodegradation of Tetracycline Hydrochloride on Self-sensitive Carbon-nitride Microspheres Enhanced by SiO₂[J]. Journal of Inorganic Materials, 2024, 39(7): 787-792.

图/表 9

图1 不同SiO2质量分数的xSiO2/SSCN的XRD谱图

Fig. 1 XRD patterns of xSiO2/SSCN with different mass fractions of SiO2

图2 不同SiO2质量分数的xSiO2/SSCN的FT-IR谱图

Fig. 2 FT-IR spectra of xSiO2/SSCN with different mass fractions of SiO2

图3 (a, b) SSCN, (c) SiO2和(d) 4% SiO2/SSCN的SEM照片

Fig. 3 SEM images of (a, b) SSCN, (c) SiO2 and (d) 4% SiO2/SSCN

图4 4% SiO2/SSCN的C、Si、Cl和O元素分布图

Fig. 4 C, Si, Cl and O elemental mappings of 4% SiO2/SSCN

图5 不同直径4% SiO2/SSCN颗粒的TEM照片

Fig. 5 TEM images of 4% SiO2/SSCN with different sizes

图6 (a)样品暗反应下对TC-HCl的吸附性能, (b) 4% SiO2/SSCN降解TC-HCl不同时间下的吸收光谱图和(c)样品对TC-HCl的可见光催化降解性能图

Fig. 6 (a) Adsorption properties of samples on TC-HCl in dark condition, (b) absorption spectra of TC-HCl photodegradation by 4% SiO2/SSCN at different time and (c) photodegradation performance of the prepared samples on TC-HCl

图7 (a)4% SiO2/SSCN光催化降解TC-HCl的循环稳定性和(b, c)光催化降解TC-HCl后4% SiO2/SSCN的SEM照片

Fig. 7 (a)Recycling property of 4% SiO2/SSCN for photocatalytic degradation of TC-HCl, (b, c) SEM images of 4% SiO2/SSCN after photocatalytic degradation of TC-HCl

图8 SSCN, SiO2 and 4% SiO2/SSCN的瞬态光电响应曲线

Fig. 8 Transient photocurrent response curves of SSCN, SiO2 and 4% SiO2/SSCN Colorful figure is available on website

图9 SSCN, SiO2 and 4% SiO2/SSCN的电化学阻抗谱图

Fig. 9 Electrochemical impedance spectra of SSCN, SiO2 and 4% SiO2/SSCN

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SiO₂增强自敏性氮化碳微球可见光降解盐酸四环素的研究

Visible-light Photodegradation of Tetracycline Hydrochloride on Self-sensitive Carbon-nitride Microspheres Enhanced by SiO₂

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