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

所属专题：【能源环境】光催化(202412)；【能源环境】污染物催化去除(202506)

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

参考文献 29

[1]	ALAGHMANDFARD A, GHANDI K. A comprehensive review of graphitic carbon nitride (g-C₃N₄)-metal oxide-based nanocomposites: potential for photocatalysis and sensing. Nanomaterials, 2022, 12(2): 294.
[2]	ZHAO B, ZHONG W, CHEN F, et al. High-crystalline g-C₃N₄ photocatalysts: synthesis, structure modulation, and H₂-evolution application. Chinese Journal of Catalysis, 2023, 52: 127.
[3]	KHARLAMOV A, BONDARENKO M, KHARLAMOVA G, et al. Synthesis of reduced carbon nitride at the reduction by hydroquinone of water-soluble carbon nitride oxide (g-C₃N₄)O. Journal of Solid State Chemistry, 2016, 241: 115.
[4]	WANG Y, LI Y, ZHAO J, et al. g-C₃N₄/B doped g-C₃N₄ quantum dots heterojunction photocatalysts for hydrogen evolution under visible light. International Journal of Hydrogen Energy, 2019, 44(2): 618.
[5]	JING L Q, XU Y G, XIE M, et al. Cyano-rich g-C₃N₄ in photochemistry: design, applications, and prospects. Small, 2024, 20: 2304404.
[6]	RUAN L W, XU G H, GU L N, et al. The physical properties of Li-doped g-C₃N₄ monolayer sheet investigated by the first-principles. Materials Research Bulletin, 2015, 66: 156.
[7]	LIU G, YAN S, SHI L, et al. The improvement of photocatalysis H₂ evolution over g-C₃N₄ with Na and cyano-group Co-modification. Frontiers in Chemistry, 2019, 7: 639.
[8]	JIANG J, CAO S, HU C, et al. A comparison study of alkali metal doped g-C₃N₄ for visible-light photocatalytic hydrogen evolution. Chinese Journal of Catalysis, 2017, 38(12): 1981.
[9]	ISMAEL M. A review on graphitic carbon nitride (g-C₃N₄) based nanocomposites: synthesis, categories, and their application in photocatalysis. Journal of Alloys and Compounds, 2020, 846(1): 15446.
[10]	ZHENG J F, XU Z, XIN S T, et al. Low-temperature molten salt synthesis of Na, K-codoped g-C₃N₄ Fenton-like catalyst with remarkable TCH degradation performance in a wide pH range. Materials Letters, 2022, 325: 132912.
[11]	MORI K, TATSUMI D, IWAMOTO T, et al. Ruthenium(ii) bipyridine nano C₃N₄ hybrids: tunable photochemical properties by using exchangeable alkali metal cations. Chemistry-An Asian Journal, 2018, 13(10): 1348.
[12]	SANO T, TSUTSUI S, KOIKE K, et al. Activation of graphitic carbon nitride (g-C₃N₄) by alkaline hydrothermal treatment for photocatalytic NO oxidation in gas phase. Journal of Materials Chemistry A, 2013, 1(21): 6489.
[13]	KUMAR A, KASHYAP S, SHARMA M, et al. Tuning the surface and optical properties of graphitic carbon nitride by incorporation of alkali metals (Na, K, Cs and Rb): effect on photocatalytic removal of organic pollutants. Chemosphere, 2022, 287: 131988.
[14]	XU Y G, GE F Y, CHEN Z G, et al. One-step synthesis of Fe-doped surface-alkalinized g-C₃N₄ and their improved visible-light photocatalytic performance. Applied Surface Science, 2019, 469: 739.
[15]	SUDRAJAT H. A one-pot, solid-state route for realizing highly visible light active Na-doped g-C₃N₄ photocatalysts. Journal of Solid State Chemistry, 2018, 257: 26.
[16]	XU Y, GONG Y, REN H, et al. In situ structural modification of graphitic carbon nitride by alkali halides and influence on photocatalytic activity. RSC Advances, 2017, 7(52): 32592.
[17]	LIU Y M, ZHANG X, WANG J P, et al. Preparation of luminescent graphitic C₃N₄ NS and their composites with RGO for property controlling. RSC Advances, 2016, 6(113): 112581.
[18]	GUAN Y H, HU S Z, GU G Z, et al. Alkali hydrothermal treatment to tynthesize hydroxyl modified g-C₃N₄ with outstanding photocatalytic phenolic compounds oxidation ability. Nano: Brief Reports and Reviews, 2024, 15(7): 1793.
[19]	ZHANG L S, DING N, HASHIMOTO M, et al. Sodium-doped carbon nitride nanotubes for efficient visible light-driven hydrogen production. Nano Research, 2018, 11(4): 2295.
[20]	XU J Y, LI Y X, PENG S Q, et al. Eosin Y-sensitized graphitic carbon nitride fabricated by heating urea for visible light photocatalytic hydrogen evolution: the effect of the pyrolysis temperature of urea. Physical Chemistry Chemical Physics, 2013, 15(20): 7657.
[21]	HU C, TSAI W F, WEI W H, et al. Hydroxylation and sodium intercalation on g-C₃N₄ for photocatalytic removal of gaseous formaldehyde. Carbon, 2021, 175: 467.
[22]	WANG X L, FANG W Q, WANG H F, et al. Surface hydrogen bonding can enhance photocatalytic H₂ evolution efficiency. Journal of Materials Chemistry A, 2013, 1(45): 14089.
[23]	LI Y X, XU H, OUYANG S, et al. In situ surface alkalinized g-C₃N₄ toward enhancement of photocatalytic H₂ evolution under visible- light irradiation. Journal of Materials Chemistry A, 2016, 4(8): 2943.
[24]	GAO H L, YAN S C, WANG J J, et al. Towards efficient solar hydrogen production by intercalated carbon nitride photocatalyst. Physical Chemistry Chemical Physics, 2013, 15(41): 18077.
[25]	SUN Z X, FISCHER J M T A, LI Q, et al. Enhanced CO₂ photocatalytic reduction on alkali-decorated graphitic carbon nitride. Applied Catalysis B: Environmental, 2017, 216: 146.
[26]	THOMMES M, KANEKO K, NEIMARK AV, et al. Physisorption of gases, three-dimensional graphene with special reference to the evaluation of surface area and pore size distribution (IUPAC technical report). Pure and Applied Chemistry, 2015, 87(10): 1051.
[27]	ZHANG Y J, MORI T, YE J H, et al. Phosphorus-doped carbon nitride solid: enhanced electrical conductivity and photocurrent generation. Journal of the American Chemical Society, 2010, 132(18): 6294.
[28]	MAIA D L S, PEPE I, DA SILVA A F, et al. Visible-light-driven photocatalytic hydrogen production over dye-sensitized β-BiTaO₄. Journal of Photochemistry and Photobiology A: Chemistry, 2012, 243: 61.
[29]	CHEN C C, MA W H, ZHAO J C. Semiconductor-mediated photodegradation of pollutants under visible-light irradiation. Chemical Society Reviews, 2010, 39(11): 4206.

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 29

相关文章 15

编辑推荐

Metrics

本文评价

[1]	江宗玉, 黄红花, 清江, 王红宁, 姚超, 陈若愚. 铝离子掺杂MIL-101(Cr)的制备及其VOCs吸附性能研究[J]. 无机材料学报, 2025, 40(7): 747-753.
[2]	柴润宇, 张镇, 王孟龙, 夏长荣. 直接组装法制备氧化铈基金属支撑固体氧化物燃料电池[J]. 无机材料学报, 2025, 40(7): 765-771.
[3]	周阳阳, 张艳艳, 于子怡, 傅正钱, 许钫钫, 梁瑞虹, 周志勇. 通过Bi³⁺自掺杂增强CaBi₄Ti₄O₁₅基陶瓷压电性能[J]. 无机材料学报, 2025, 40(6): 719-728.
[4]	陈莉波, 盛盈, 伍明, 宋季岭, 蹇建, 宋二红. Na和O元素共掺杂氮化碳高效光催化制氢[J]. 无机材料学报, 2025, 40(5): 552-562.
[5]	孙雨萱, 王政, 时雪, 史颖, 杜文通, 满振勇, 郑嘹赢, 李国荣. 缺陷偶极子热稳定性对Fe掺杂PZT陶瓷机电性能影响研究[J]. 无机材料学报, 2025, 40(5): 545-551.
[6]	安然, 林锶, 郭世刚, 张冲, 祝顺, 韩颖超. 铁掺杂纳米羟基磷灰石的制备及紫外吸收性能研究[J]. 无机材料学报, 2025, 40(5): 457-465.
[7]	渠吉发, 王旭, 张维轩, 张康喆, 熊永恒, 谭文轶. 掺杂改性NaYTiO₄增强固体氧化物燃料电池阳极抗硫中毒性能[J]. 无机材料学报, 2025, 40(5): 489-496.
[8]	穆浩洁, 张源江, 喻彬, 付秀梅, 周世斌, 李晓东. ZrO₂掺杂Y₂O₃-MgO纳米复相陶瓷的制备及性能研究[J]. 无机材料学报, 2025, 40(3): 281-289.
[9]	沈浩, 陈倩倩, 周渤翔, 唐晓东, 张媛媛. A位La/Sr共掺杂PbZrO₃薄膜的制备及储能特性优化[J]. 无机材料学报, 2024, 39(9): 1022-1028.
[10]	程俊, 张家伟, 仇鹏飞, 陈立东, 史迅. P掺杂β-FeSi₂材料的制备与热电输运性能[J]. 无机材料学报, 2024, 39(8): 895-902.
[11]	赵志翰, 郭鹏, 魏菁, 崔丽, 刘山泽, 张文龙, 陈仁德, 汪爱英. Ti-DLC薄膜压阻性能及载流子输运行为研究[J]. 无机材料学报, 2024, 39(8): 879-886.
[12]	李家琪, 李小松, 李煊赫, 朱晓兵, 朱爱民. 暖等离子体合成过渡金属掺杂氧化锰析氧电催化剂[J]. 无机材料学报, 2024, 39(7): 835-844.
[13]	TAM YU Puy Mang, 徐愉, 高泉浩, 周海琼, 张振, 尹浩, 李真, 吕启涛, 陈振强, 马凤凯, 苏良碧. 掺铒CaF₂、SrF₂、PbF₂晶体的光谱性能与团簇结构研究[J]. 无机材料学报, 2024, 39(3): 330-336.
[14]	李宪珂, 张超逸, 黄林, 孙鹏, 刘波, 徐军, 唐慧丽. 高质量铟掺杂氧化镓单晶浮区法生长研究[J]. 无机材料学报, 2024, 39(12): 1384-1390.
[15]	戴乐, 刘洋, 高轩, 王书豪, 宋雅婷, 唐明猛, 刘丽莎, 汪尧进. 浓度梯度掺杂实现BiFeO₃薄膜自极化[J]. 无机材料学报, 2024, 39(1): 99-106.