二维g-C3N4与Ag-TiO2复合光催化剂降解气态乙醛抗失活研究

doi:10.15541/jim20220123

无机材料学报 ›› 2022, Vol. 37 ›› Issue (8): 865-872.DOI: 10.15541/jim20220123 CSTR: 32189.14.10.15541/jim20220123

所属专题：【能源环境】光催化(202312)；【信息功能】MAX层状材料、MXene及其他二维材料(202409)

二维g-C₃N₄与Ag-TiO₂复合光催化剂降解气态乙醛抗失活研究

薛虹云¹^,²(), 王聪宇¹, MAHMOOD Asad¹(), 于佳君¹^,², 王焱¹, 谢晓峰¹, 孙静¹()

1.中国科学院上海硅酸盐研究所高性能陶瓷与超细微结构国家重点实验室, 上海 200050
2.中国科学院大学, 北京 100049

收稿日期:2022-03-07 修回日期:2022-04-05 出版日期:2022-08-20 网络出版日期:2022-04-26
通讯作者: MAHMOOD Asad. E-mail: amkhan036@yahoo.com;
孙静, 研究员. E-mail: jingsun@mail.sic.ac.cn
作者简介:薛虹云(1998-), 女, 硕士研究生. E-mail: hyxue0310@163.com

Two-dimensional g-C₃N₄ Compositing with Ag-TiO₂ as Deactivation Resistant Photocatalyst for Degradation of Gaseous Acetaldehyde

XUE Hongyun¹^,²(), WANG Congyu¹, MAHMOOD Asad¹(), YU Jiajun¹^,², WANG Yan¹, XIE Xiaofeng¹, SUN Jing¹()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2022-03-07 Revised:2022-04-05 Published:2022-08-20 Online:2022-04-26
Contact: MAHMOOD Asad. E-mail: amkhan036@yahoo.com;
SUN Jing, professor. jingsun@mail.sic.ac.cn
About author:XUE Hongyun (1998-), female, Master candidate. E-mail: hyxue0310@163.com
Supported by:
Key Collaborative Research Program of the Alliance of International Science Organizations(ANSO-CR-KP-2020-13);National Key Research and Development Program of China(2021YFE0110400);National Natural Science Foundation of China(41907303);National Natural Science Foundation of China(52072387);Shanghai Commission of Science and Technology Program(19DZ1202600);Shanghai Commission of Science and Technology Program(20DZ1204100);State Key Laboratory Director Fund of SICCAS(Y9ZC0102)

摘要/Abstract

摘要：

光催化剂失活是影响其在去除低浓度VOCs的实际应用中的主要因素之一。本研究将TiO₂与2D石墨碳氮化碳(g-C₃N₄)复合, 显著提高了光催化剂的稳定性。当Ag改性的Ag-TiO₂(AT)用于降解乙醛气体时, 反应60 min后开始发生失活现象, 反应延长至400 min则完全失活。而AT与g-C₃N₄复合改性后的样品g-C₃N₄/ Ag-TiO₂(CAT)具有优异的光催化性能和稳定性, 反应至600 min未发生失活。原位FT-IR、PL和光电流的研究表明, 当AT催化降解乙醛时, 反应中间体会在表面积累导致催化剂失活。而引入的g-C₃N₄可以为中间体提供更多的吸附位点, 从而提高稳定性。此外, 引入g-C₃N₄还有利于电荷分离和产生活性氧物种, 促进乙醛和中间体降解。本研究揭示了2D材料在开发稳定可持续降解VOCs的光催化剂方面的实用性。

关键词: 光催化, 二氧化钛, g-C₃N₄, 抗失活, 原位漫反射红外光谱

Abstract:

The photocatalysts deactivation is one of the major issues, which lowers the usefulness of photocatalytic oxidation technology for the removal of low content volatile organic compounds (VOCs). Here, we carried out a series of experiments to demonstrate that the photocatalysts stability could be significantly improved via coupling the oxide base semiconductors, i.e., TiO₂ with 2D materials such as graphitic carbon nitride (g-C₃N₄). Initially, when Ag modified TiO₂ (AT) was used for the gaseous acetaldehyde degradation, a robust deactivation was observed within 60 min. The AT catalyst completely lost its activity when the reaction time was extended to 400 min. On the contrary, the g-C₃N₄ modified AT (CAT) showed superior photocatalytic performance and improved stability (600 min). The in-situ FT-IR, PL, and photocurrent studies suggested that the accumulation of reaction intermediates in the case of AT fundamentally caused the deactivation. However, the g-C₃N₄ provided excessive adsorption sites for the reaction by-products which improved the stability. Additionally, the PL and ESR studies suggested that the existence of g-C₃N₄ improved the charge separation and production of reactive oxygen species, which facilitated the photodegradation of acetaldehyde and ultimate reaction products. This study realizes the usefulness of 2D materials for developing stable and visible light active photocatalysts for applications in sustainable VOC abatement technology.

Key words: photocatalysis, titanium dioxide, g-C₃N₄, deactivation-resistant, in-situ diffuse reflectance infrared Fourier transform spectroscopy

中图分类号:

TQ174

薛虹云, 王聪宇, MAHMOOD Asad, 于佳君, 王焱, 谢晓峰, 孙静. 二维g-C₃N₄与Ag-TiO₂复合光催化剂降解气态乙醛抗失活研究[J]. 无机材料学报, 2022, 37(8): 865-872.

XUE Hongyun, WANG Congyu, MAHMOOD Asad, YU Jiajun, WANG Yan, XIE Xiaofeng, SUN Jing. Two-dimensional g-C₃N₄ Compositing with Ag-TiO₂ as Deactivation Resistant Photocatalyst for Degradation of Gaseous Acetaldehyde[J]. Journal of Inorganic Materials, 2022, 37(8): 865-872.

图/表 7

Fig. 1 Activation maintained by CAT for gaseous acetaldehyde (a) Adsorption, photodegradation and CO2 generation curves of acetaldehyde gas by AT and CAT samples; (b) Photocatalytic degradation of acetaldehyde by AT sample under visible light irradiation for 400 min and CAT sample under visible light irradiation for 600 min; (c) XRD patterns of AT and CAT samples before and after degradation of acetaldehyde gas (160 min) under visible light irradiation; (d) Photocatalytic degradation of acetaldehyde by AT sample under visible light irradiation for 360 min, and cutting off acetaldehyde inlet at 180 min

Fig. 2 In-situ DRIFTS spectra of (a) AT and (b) CAT photocatalysts degrading acetaldehyde gas under visible light irradiation, and (c) photocatalytic reaction routes of acetaldehyde

Fig. 3 Photocurrent and PL plots of the photocatalytic degradation of acetaldehyde (a) Photocurrent and (c) PL plots of AT sample for the photocatalytic degradation of acetaldehyde under visible light irradiation; (b) Photocurrent and (d) PL plots of the photocatalytic degradation of acetaldehyde by CAT sample under visible light irradiation for 300 min 0, 60, 120, 180 min represent the photocatalytic reaction time of which the dotted lines of 240 and 300 min represent 1 and 2 h, respectively, when acetaldehyde was stopped but the light was kept on

Fig. 4 ESR profiles of (a, c) DMPO-•O2- and (b, d) DMPO-•OH for the photocatalytic degradation of acetaldehyde by AT(a, b) and CAT (c, d) sample Under visible light irradiation for 300 min 0, 60, 120, 180 min represent the photocatalytic reaction time, of which the dotted lines of 240 and 300 min represent 1 and 2 h, respectively, when acetaldehyde was stopped but the light was kept on

Fig. 5 Schematic of photocatalytic reaction mechanism

Table S1 Assignment of FT-IR bands observed for AT sample in the process of dark adsorption and photocatalytic degradation for acetaldehyde

Product	Wavenumber/cm^-1	Mode of vibration
1	1072	β(CH₃)
2	1128, 1166	v(C-C)
3	1315	δ(CH₃)
4	1339	δ_as(CH₃)
5	1377	v_s(COO)
6	1419	δ_s(CH₃)
7	1458, 1473	δ(CH₂)
8	1541, 1558	v_as(COO)
9	1603	v(C=C)
10	1732, 1716, 1699, 1650	v(C=O)

Table S2 Assignment of FT-IR bands observed for CAT sample in the process of dark adsorption and photocatalytic degradation for acetaldehyde

Product	Wavenumber/cm^-1	Mode of vibration
1	1050, 1100	β(CH₃)
2	1200	r(CH₂)
3	1221, 1294	v(C-O)
4	1316	δ(CH₃)
5	1339, 1371	v_s(COO)
6	1361	δ(CH)
7	1419	δ_s(CH₃)
8	1458	δ(CH₂)
9	1522, 1558,1573	v_as(COO)
10	1620	v(C=C)
11	1771, 1732, 1716, 1699, 1650	v(C=O)

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二维g-C₃N₄与Ag-TiO₂复合光催化剂降解气态乙醛抗失活研究

Two-dimensional g-C₃N₄ Compositing with Ag-TiO₂ as Deactivation Resistant Photocatalyst for Degradation of Gaseous Acetaldehyde

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