Na+/g-C3N4材料的制备及光催化降解亚甲基蓝机理

doi:10.15541/jim20240142

无机材料学报 ›› 2024, Vol. 39 ›› Issue (10): 1143-1150.DOI: 10.15541/jim20240142 CSTR: 32189.14.10.15541/jim20240142

Na⁺/g-C₃N₄材料的制备及光催化降解亚甲基蓝机理

李秋实¹(), 殷广明¹^,²(), 吕伟超¹, 王怀尧², 李婧琳², 杨红光², 关芳芳²

1.齐齐哈尔大学分析测试中心, 齐齐哈尔 161006
2.齐齐哈尔大学化学与化学工程学院, 齐齐哈尔 161006

收稿日期:2024-03-22 修回日期:2024-05-31 出版日期:2024-10-20 网络出版日期:2024-10-09
通讯作者: 殷广明, 正高级实验师. E-mail: qdyingm@163.com
作者简介:李秋实(1993-), 男, 硕士. E-mail: hcgz116@163.com
基金资助:
黑龙江省省属高等学校基本科研业务费(135509106)

Preparation of Na⁺/g-C₃N₄ Materials and Their Photocatalytic Degradation Mechanism on Methylene Blue

LI Qiushi¹(), YIN Guangming¹^,²(), LÜ Weichao¹, WANG Huaiyao², LI Jinglin², YANG Hongguang², GUAN Fangfang²

1. Analysis and Test Center, Qiqihaer University, Qiqihaer 161006, China
2. College of Chemistry and Chemical Engineering, Qiqihaer University, Qiqihaer 161006, China

Received:2024-03-22 Revised:2024-05-31 Published:2024-10-20 Online:2024-10-09
Contact: YIN Guangming, professor. E-mail: qdyingm@163.com
About author:LI Qiushi (1993-), male, Master. E-mail: hcgz116@163.com
Supported by:
Fundamental Research Funds in Heilongjiang Province Universities(135509106)

摘要/Abstract

摘要：

制备碱金属掺杂的g-C₃N₄在g-C₃N₄半导体光催化材料研究中属于一个重要分支。本研究采用溶液合成、煅烧和溶剂热反应方法制备了Na⁺掺杂的g-C₃N₄样品(Na⁺/g-C₃N₄), 通过不同检测手段确定了Na⁺在g-C₃N₄中的负载位置和光电性能, 考察了样品的形貌、比表面积及孔径随溶剂热反应时间延长的变化规律。结果表明：Na⁺负载位置和表面生成的C-O^-基团增强了g-C₃N₄材料的物理和化学吸附性能, Na⁺/g-C₃N₄对亚甲基蓝(MB)的吸附率最高可达到93.25%; Na⁺负载位置对g-C₃N₄的π共轭体系的电子分布产生影响, 进而改变了材料的禁带宽度(E_g)、导(价)带位置和光生载流子分离效率及传输速率; 在可见光降解过程中, 由于MB的自身光敏性和在Na⁺/g-C₃N₄样品表面的强吸附性, MB和Na⁺/g-C₃N₄样品构建了独特的光敏-光催化降解体系, MB不仅通过光敏自降解, 还在Na⁺/g-C₃N₄协同下进行了光催化降解。在pH 6.0条件下, MB和Na⁺/g-C₃N₄光催化体系对MB的最高降解率可达96.40%。

关键词: 石墨相碳化氮, Na⁺, 掺杂, 光敏化, 光催化机理

Abstract:

Preparation of alkali metal doped g-C₃N₄ materials is an important branch in the research of g-C₃N₄ semiconductor photocatalytic materials. However, there is still lack of study on g-C₃N₄ materials revealing mechanisms in photosensitizer-assisted photocatalytic degradation. In this study, Na⁺ doped g-C₃N₄ photocatalysts (Na⁺/g-C₃N₄) were prepared using solution synthesis, calcination, and solvothermal reaction methods.The doped position of Na⁺ in g-C₃N₄ and photoelectric performance were determined. The changes of morphological, specific surface area, and pore size of Na⁺/g-C₃N₄ materials were analyzed by scanning electron microscopy, N₂ adsorption and desorption experiments. In Na⁺/g-C₃N₄ materials, the Na⁺loaded in a cyclic structure composed of three heptazine structural units, coordinating with N atoms. Na⁺/g-C₃N₄ changed the adsorption performance of g-C₃N₄, altered its bandgap width and position of conduction (valence) band, and increased its separation rate of photogenerated electrons and holes and charge transport rate of the material by affecting the π-conjugated system of g-C₃N₄. During the solvothermal reaction process for synthesis of Na⁺/g-C₃N₄, strong hydrolysis caused decomposition of unstable structures of g-C₃N₄while the C-O^- bonds were formed at the edge of g-C₃N₄. The physical and chemical adsorption sites for methylene blue (MB) of Na⁺/g-C₃N₄ materials are confirmed by π-conjugated system and C-O^- bonds of Na⁺/g-C₃N₄, by which Na⁺/g-C₃N₄ materials can adsorb MB up to 93.25%, in contrast to the g-C₃N₄ materials’ adsorbtion only up to 24.50%. Under visible light irradiation, due to their strong adsorption capacity and photosensitivity to MB, Na⁺/g-C₃N₄ materials have constructed a unique photosensitive- photocatalytic degradation system with MB. MB not only acts as the photosensitizer for self degradation but also collaborates with Na⁺/g-C₃N₄ materials for photocatalytic degradation. At pH 6.0, the maximum degradation rate of MB is up to 96.40% in the photosensitive-photocatalytic system constructed with MB and Na⁺/g-C₃N₄ samples.

Key words: g-C₃N₄, Na⁺, doping, photosensitization, photocatalytic mechanism

中图分类号:

O649

李秋实, 殷广明, 吕伟超, 王怀尧, 李婧琳, 杨红光, 关芳芳. Na⁺/g-C₃N₄材料的制备及光催化降解亚甲基蓝机理[J]. 无机材料学报, 2024, 39(10): 1143-1150.

LI Qiushi, YIN Guangming, LÜ Weichao, WANG Huaiyao, LI Jinglin, YANG Hongguang, GUAN Fangfang. Preparation of Na⁺/g-C₃N₄ Materials and Their Photocatalytic Degradation Mechanism on Methylene Blue[J]. Journal of Inorganic Materials, 2024, 39(10): 1143-1150.

图/表 13

图1 样品的XRD(a)和FT-IR(b)谱图

Fig. 1 XRD patterns (a) and FT-IR spectra (b) of samples

图2 样品的XPS图谱

Fig. 2 XPS spectra of samples (a) Survey spectra; (b) C1s; (c) N1s; (d) O1s; (e) Na1s

图3 样品的SEM照片

Fig. 3 SEM images of samples (a) g-C3N4; (b) 2-Na+/g-C3N4; (c) 4-Na+/g-C3N4; (d) 6-Na+/g-C3N4

图4 不同样品的N2吸脱附等温线

Fig. 4 N2 adsorption-desorption isotherms of different samples

图5 样品的I-t曲线(a), EIS的Nyquist曲线(b)和PL谱图(c)

Fig. 5 I-t curves (a), EIS Nyquist plots (b) and PL spectra (c) of samples

图6 样品对MB的光催化降解率(a)和4-Na+/g-C3N4光催化循环测试结果(b)

Fig. 6 Photocatalytic degradation rates of samples on MB (a) and photocatalytic recycling testing of 4-Na+/g-C3N4 (b)

图7 样品对MB的吸附率(a)和光降解前后的FT-IR谱图(b)

Fig. 7 Adsorption rates on MB of different samples (a) and FT-IR spectra before and after photodegradation (b)

图8 样品的UV-DRS谱图(a)和Mott-Schottky曲线(b)

Fig. 8 UV-DRS spectra (a) and Mott-Schottky curves (b) of samples

图9 捕获实验效果(a)和光催化降解机理示意图(b)

Fig. 9 Photodegradation efficiencies with different capture agents (a) and schematic diagram of photodegradation process (b)

图S1 g-C3N4水解的反应式

Fig. S1 Reaction scheme of hydrolysis of g-C3N4

图S2 样品的孔径分布图

Fig. S2 Pore size distribution of different samples

图S3 不同用量4-Na+/g-C3N4的光催化效果对比图

Fig. S3 Comparison of photocatalytic effects of 4-Na+/g-C3N4 at different dosages

图S4 不同pH条件下4-Na+/g-C3N4光催化效果对比图

Fig. S4 Comparison of photocatalytic effects of 4-Na+/g-C3N4 at different pH

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Na⁺/g-C₃N₄材料的制备及光催化降解亚甲基蓝机理

Preparation of Na⁺/g-C₃N₄ Materials and Their Photocatalytic Degradation Mechanism on Methylene Blue

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