g-C3N4/TiO2异质结光催化剂的制备及其对NO的降解性能

doi:10.16085/j.issn.1000-6613.2024-0583

摘要/Abstract

摘要：

对石墨相氮化碳（g-C₃N₄，CN）进行改性是提高其光催化性能的重要手段。采用热聚合法以硫脲为前体制备了S掺杂氮化碳（SCN），以石墨相氮化碳、S掺杂氮化碳和TiO₂作为光催化剂的主要组分，制备了二元异质结复合光催化剂CN-Ti和SCN-Ti，利用X射线衍射、扫描电子显微镜、X射线光电子能谱、比表面积、紫外可见漫反射、电化学测试等表征手段分析了光催化剂的形貌、结构、光学和电化学性能，通过对NO的降解评价了其光催化性能，根据自由基捕获实验进一步研究了其光催化降解机理。结果表明，二元异质结复合光催化剂SCN-Ti具有更优的光催化性能，SCN和TiO₂质量比为5∶5时所得的光催化剂SCN-Ti-50在紫外光和可见光条件下对NO的降解率最高，分别可达84.9%和57.1%，显著高于CN在紫外光和可见光下对NO的降解率（分别为61.7%和44.2%），且经5次循环后，其仍具有良好的光催化活性。光催化活性的提高主要归因于SCN和TiO₂构建的Ⅱ型异质结促进了载流子分离，提高了降解NO活性物质光生电子、空穴和 $· O 2 -$ 的生成效率。本文为拓宽g-C₃N₄在光催化领域的应用提供了可借鉴的思路。

关键词: 石墨相氮化碳, 光催化, NO降解, 二氧化钛异质结, S掺杂氮化碳

Abstract:

Modification of graphite phase carbon nitride (g-C₃N₄, CN) is an important means to improve its photocatalytic performance. S-doped carbon nitride (SCN) was prepared by thermal polymerization with thiourea as the precursor, and binary heterojunction composite photocatalysts CN-Ti and SCN-Ti were prepared with graphite phase carbon nitride, S-doped carbon nitride and TiO₂ as the main components. The morphology, structure, optical and electrochemical properties of the photocatalyst were analyzed by X-ray diffraction, scanning electron microscope, X-ray photoelectron spectroscopy, specific surface area, ultraviolet-visible diffuse reflectance and electrochemical test, and their photocatalytic performance were evaluated by degradation of NO. According to the free radical capture experiment, the photocatalytic degradation mechanism was further studied. The results showed that the binary heterojunction composite photocatalyst SCN-Ti had better photocatalytic performance. When the mass ratio of SCN∶TiO₂ was 5∶5, the photocatalytic NO degradation rate was the highest, reaching 84.9% and 57.1% under ultraviolet light and visible light, respectively, which was significantly higher than that of CN (61.7% and 44.2%, respectively), and after five cycles, it still had good photocatalytic activity. The improvement of photocatalytic activity was mainly attributed to the type Ⅱ heterojunction constructed by SCN and TiO₂, which promoted carrier separation and improved the generation efficiency of photogenerated electrons, holes and $· O 2 -$ free radicals that degraded NO active substances. This study provided a reference for broadening the application of g-C₃N₄ in the field of photocatalysis.

Key words: graphite phase carbon nitride, photocatalysis, NO degradation, titanium dioxide heterojunction, S-doped carbon nitride

中图分类号:

O613

张佩, 高莉宁, 丁思晴, 李立, 祝锡爇, 何锐. g-C₃N₄/TiO₂异质结光催化剂的制备及其对NO的降解性能[J]. 化工进展, 2025, 44(4): 2045-2056.

ZHANG Pei, GAO Lining, DING Siqing, LI Li, ZHU Xiruo, HE Rui. Preparation of g-C₃N₄/TiO₂ heterojunction catalyst and its photocatalytic NO degradation performance[J]. Chemical Industry and Engineering Progress, 2025, 44(4): 2045-2056.

图/表 15

图1 自组装光催化降解装置

表1 光催化降解实验参数和灯管技术参数

污染气体量	流量	相对湿度	检测时间	紫外光波长	日光灯
35mg/m³	1L/min	50%	每小时1次，共5h	365nm	白光

图2 光催化剂的XRD谱图

图3 光催化剂的SEM图

图4 光催化剂的XPS谱图

图5 光催化剂的吸附-脱附等温线和孔径分布

表2 光催化剂的比表面积

光催化剂	平均孔径/nm	总孔容/cm³·g^-1	比表面积/m²·g^-1
TiO₂	29.16	0.015	5.59
CN	22.38	0.011	5.77
SCN	30.12	0.024	10.40
CN-Ti-30	19.92	0.015	8.43
CN-Ti-50	17.72	0.016	9.65
CN-Ti-60	25.61	0.024	12.08
SCN-Ti-30	28.75	0.024	10.79
SCN-Ti-50	18.72	0.024	11.46
SCN-Ti-60	26.94	0.026	12.25

图6 光催化剂的UV-Vis DRS图

图7 光催化剂的PL图、瞬态光电流响应和EIS图

表3 光催化剂的阻抗

光催化剂	R_s/kΩ	R_ct/MΩ
TiO₂	7.714	47.24
CN	10.800	42.73
SCN	8.153	40.92
CN-Ti-50	9.568	38.05
SCN-Ti-50	8.992	35.42

图8 光催化剂在紫外光和可见光下对NO的降解率

图9 光催化剂在紫外光和可见光下的降解稳定性曲线

图10 光催化NO前后的SCN-Ti-50光催化剂的XPS谱图

图11 自由基捕获实验结果

图12 SCN-Ti-50光催化降解NO机理

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g-C₃N₄/TiO₂异质结光催化剂的制备及其对NO的降解性能

Preparation of g-C₃N₄/TiO₂ heterojunction catalyst and its photocatalytic NO degradation performance

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