g-C<sub>3</sub>N<sub>4</sub>/POPs异质结制备及其可见光催化性能

郭佳允; 傅炀杰; 张柯杰; 姬云; 杨娟; 王齐

doi:10.13801/j.cnki.fhclxb.20220325.001

g-C₃N₄/POPs异质结制备及其可见光催化性能

doi: 10.13801/j.cnki.fhclxb.20220325.001

郭佳允¹,
傅炀杰¹,
张柯杰¹,
姬云¹,
杨娟³,
王齐^{1, 2, ,}

1.
浙江工商大学　环境科学与工程学院，杭州 310018
2.
浙江师范大学　“先进催化材料”教育部重点实验室，金华 321004
3.
河南理工大学　安全科学与工程学院，郑州 450018

基金项目: 国家自然科学基金(21876154；52074103)；浙江师范大学“先进催化材料”教育部重点实验室和浙江省“固体表面反应化学”重点实验室开放课题(KLMEACM202104)National Natural Science Foundation of China (21876154; 52074103); Open Research Fund of Key Laboratory of the Ministry of Education for Advanced Catalysis Materials and Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Zhejiang Normal University (KLMEACM202104)

详细信息

通讯作者:
王齐，博士，教授，博士生导师，研究方向为环境光催化　 E-mail：wangqi8327@zjgsu.edu.cn

中图分类号: O643.36
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出版历程
- 收稿日期: 2022-01-10
- 修回日期: 2022-03-10
- 录用日期: 2022-03-19
- 网络出版日期: 2022-03-28
- 刊出日期: 2023-02-15

Preparation and visible light catalytic performance of g-C₃N₄/POPs heterojunction

GUO Jiayun¹,
FU Yangjie¹,
ZHANG Kejie¹,
JI Yun¹,
YANG Juan³,
WANG Qi^{1, 2
, ,}

1.
School of Environment Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018, China
2.
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua 321004, China
3.
College of Safety and Engineering, Henan Polytechnic University, Zhengzhou 450018, China

摘要

摘要: 光催化技术是一种极具应用前景的环境修复技术，开发高效、稳定、具有可见光响应的光催化剂是其研究的重点之一。本文采用常压溶剂热法，以1, 3, 5-三(4-氨基苯基)苯(TAPB)和2, 5-二甲氧基苯-1, 4二甲醛(DMTP)为单体合成的共轭多孔有机聚合物TAPB-DMTP POP为基底，原位负载不同比例的g-C₃N₄，制备g-C₃N₄/POPs复合光催化剂。通过XRD、FTIR、BET、TGA、UV-Vis DRS、电流-时间(i-t)和EIS等测试方法表征了g-C₃N₄/POPs的化学结构与光学特性。在可见光条件下，选择Cr(VI)为模型污染物探究了不同g-C₃N₄负载量的g-C₃N₄/POPs光催化还原效率，并对pH值、催化剂用量和底物浓度等影响因素进一步探究。结果表明：在pH=2条件下，g-C₃N₄/POP-2表现出了最佳的光催化还原性能，可见光光照下，30 min还原效率达到99.1%，Cr(VI)还原效率相对g-C₃N₄和TAPB-DMTP POP显著提高，其拟合一级动力学速率常数分别为纯g-C₃N₄和TAPB-DMTP POP的22.0倍和2.2倍。同时该材料5次循环后对Cr(VI)还原率仍然达到90%以上，具有优良的光催化稳定性。
- 多孔有机聚合物 /
- g-C₃N₄ /
- 异质结 /
- 光催化 /
- Cr(VI)还原
Abstract: As a promising environmental remediation technology, the development of efficient and stable photocatalysts with visible light response is one of the important studies in photocatalysis technology. In this work, g-C₃N₄/porous organic polymers (POPs) composite photocatalysts were prepared via atmospheric solvothermal method. Different ratios of g-C₃N₄ were in-situ loaded on conjugated porous organic polymers TAPB-DMTP POP synthesized with 1, 3, 5-tris(4-aminophenyl) benzene (TAPB) and 2, 5-dimethoxybenzene-1, 4-diformaldehyde (DMTP) as monomers. The chemical structure and optical properties of g-C₃N₄/POPs materials were characterized by XRD, FTIR, BET, TGA, UV-Vis DRS, current-time (i-t) and EIS methods. Cr(VI) was selected as the model pollutant, the photocatalytic reduction activities of g-C₃N₄/POPs photocatalysts with different g-C₃N₄ loading ratios were explored under visible light conditions, and the effects of pH value, catalyst dosage and substrate concentration were further investigated. The results shows that g-C₃N₄/POP-2 exhibits the best photocatalytic reduction performance at pH=2 with the reduction efficiency of 99.1% after 30 min of visible illumination. The reduction efficiency of Cr(VI) is significantly improved over g-C₃N₄/POP-2 compared with pure g-C₃N₄ and TAPB-DMTP POP, and the fitted first-order kinetics rate are 22.0 times and 2.2 times that of g-C₃N₄ and TAPB-DMTP POP, respectively. This composite also exhibits excellent photocatalytic stability as the Cr(VI) reduction rate reaches more than 90% after five cycles.
- porous organic polymers (POPs) /
- g-C₃N₄ /
- heterojunction /
- photocatalytic /
- Cr(VI) reduction

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图 1 石墨相氮化碳(g-C₃N₄)、g-C₃N₄/POP和多孔有机聚合物1, 3, 5-三(4-氨基苯基)苯-2, 5-二甲氧基苯-1, 4-二甲醛(TAPB-DMTP POP)的XRD图谱

Figure 1. XRD patterns of graphitic carbon nitride (g-C₃N₄), g-C₃N₄/POP and porous organic polymer 1, 3, 5-tris(4-aminophenyl)benzene-2, 5-dimethoxybenzene-1, 4-diformaldehyde (TAPB-DMTP POP)

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图 2 g-C₃N₄、反应前后的g-C₃N₄/POP、TAPB-DMTP POP、TAPB和DMTP的红外图谱

Figure 2. FTIR spectra of g-C₃N₄, g-C₃N₄/POP before and after the reaction, TAPB-DMTP POP, TAPB and DMTP

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图 3 g-C₃N₄、反应前后的g-C₃N₄/POP和TAPB-DMTP POP的N₂吸附-脱附曲线

Figure 3. N₂ adsorption-desorption curves of g-C₃N₄, g-C₃N₄/POP before and after the reaction and TAPB-DMTP POP

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图 4 g-C₃N₄、g-C₃N₄/POP和TAPB-DMTP POP的热重曲线

Figure 4. TGA curves of g-C₃N₄, g-C₃N₄/POP and TAPB-DMTP POP

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图 5 g-C₃N₄、g-C₃N₄/POP和TAPB-DMTP POP的紫外-可见漫反射光谱(插图：带隙图)

Figure 5. UV-Vis DRS of g-C₃N₄, g-C₃N₄/POP and TAPB-DMTP POP (Insert: Band gap)

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图 6 不同条件下光催化还原Cr(VI)动力学曲线

k—Rate constant

Figure 6. Kinetic curves of photocatalytic reduction of Cr(VI) under different conditions

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图 7 pH值、Cr(VI)浓度和催化剂浓度对光催化去除率的影响

C_{initial Cr(VI)}—Cr(VI) concentration; C_catalyst—Catalyst concentration

Figure 7. Influence of pH value, Cr(VI) concentration and catalyst concentration on photocatalytic removal rate

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图 8 g-C₃N₄/POP-2还原Cr(VI)的循环使用性能

Figure 8. Reusability of g-C₃N₄/POP-2 for the photocatalytic reduction of Cr(VI)

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图 9 g-C₃N₄、g-C₃N₄/POP和TAPB-DMTP POP的瞬态光电流曲线(a)和阻抗谱(b)(插图：等效电路)

R_s—Electrolyte solution resistance; R_p—Resistance of electrode to electrolyte interface charge transfer; CPE—Constant phase angle element

Figure 9. Transient photocurrent curves (a) and EIS Nyquist plots (b) (Inset: Equivalent circuit) of g-C₃N₄, g-C₃N₄/POP and TAPB-DMTP POP

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图 10 (a) g-C₃N₄、g-C₃N₄/POP和TAPB-DMTP POP的Mott-Schottky曲线；(b) g-C₃N₄/POP光催化还原Cr(VI)机制图

C—Capacitance; E_g—Band gap; CB—Conduction band; VB—Valence band; EDTA-2Na—Ethylenediamine tetracetic acid sodium

Figure 10. (a) Mott-Schottky plots of g-C₃N₄, g-C₃N₄/POP and TAPB-DMTP POP; (b) Proposed mechanism of photocatalytic Cr(VI) reduction by g-C₃N₄/POP

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表 1 g-C₃N₄/POP复合材料具体配比

Table 1. Specific composition ratios of g-C₃N₄/POP composites

Sample	g-C₃N₄ content/wt%
g-C₃N₄/POP-1	5.0
g-C₃N₄/POP-2	9.4
g-C₃N₄/POP-3	13.5
Note: POP—Porous organic polymers.

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