碳量子点修饰g-C3N4/SnO2复合材料光催化性能

doi:10.16085/j.issn.1000-6613.2020-0647

化工进展 ›› 2021, Vol. 40 ›› Issue (2): 908-916.DOI: 10.16085/j.issn.1000-6613.2020-0647

碳量子点修饰g-C₃N₄/SnO₂复合材料光催化性能

何源¹^,²(), 许磊¹^,⁴(), 夏仡³, 王学谦², 刚瑞奇¹, 王郎郎²

^1.昆明理工大学冶金与能源工程学院，云南昆明 650093
^2.昆明理工大学环境科学与工程学院，云南昆明 650093
^3.昆明理工大学分析测试中心，云南昆明 650093
^4.云南省部共建复杂有色金属资源清洁利用国家重点实验室，云南昆明 650093

收稿日期:2020-04-23 修回日期:2020-06-11 出版日期:2021-02-05 发布日期:2021-02-09
通讯作者: 许磊
作者简介:何源（1994—），男，硕士研究生，研究方向为光催化降解有机染料。E-mail：1534096669@qq.com。
基金资助:
国家自然科学基金(51864030);云南省科技人才计划(2019HB003);云南省万人计划青年拔尖人才;云南省重大科技专项(2018ZE027);昆明理工大学自然科学基金(KKSY201732033)

Photocatalytic performance of carbon quantum dots modified g-C₃N₄/SnO₂ composites

Yuan HE¹^,²(), Lei XU¹^,⁴(), Yi XIA³, Xueqian WANG², Ruiqi GANG¹, Langlang WANG²

^1.Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
^2.Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
^3.Kunming University of Science and Technology Analysis and Testing Center, Kunming 650093, Yunnan, China
^4.State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization in Yunnan Province, Kunming 650093, Yunnan, China

Received:2020-04-23 Revised:2020-06-11 Online:2021-02-05 Published:2021-02-09
Contact: Lei XU

摘要/Abstract

摘要：

以四氯化锡五水合物、乙二醇和氨水为原料，在微波辅助水热条件下快速合成氧化锡纳米颗粒，以尿素为前体在马弗炉中退火得到g-C₃N₄，使用柠檬酸和乙二胺为原料水热合成碳量子点。室温下，将碳量子点/ g-C₃N₄/SnO₂在通风橱中进行搅拌得到碳量子点负载的氮化碳/氧化锡复合材料。通过透射电子显微镜（TEM）、 X射线衍射（XRD）、氮气吸附-解吸等温线（BET）、紫外-可见分光光度计（UV-vis）、电子自旋（顺磁）共振波谱仪（ESR）对复合材料的形貌、结构特征、吸光度和光催化过程中的活性物质等进行表征和分析，并通过在紫外光下降解罗丹明B（RhB）测试样品的光催化性能。试验结果表明，紫外-可见分光光谱吸收边缘的红移说明碳量子点负载后能提高复合材料在可见光区域的响应，光催化试验表明碳量子点负载能提高g-C₃N₄/SnO₂复合材料的光催化性能，当碳量子点负载量为7%时复合材料的降解效率最高，在3h内对RhB的降解效率为97%。此外，微波辅助水热法能在短时间内大量合成氧化锡纳米颗粒，且氧化锡纳米颗粒具有较小的晶粒尺寸（8.5nm），可以高效制备并应用于环保领域。

关键词: 碳量子点, 氮化碳/氧化锡, 复合材料, 光催化, 降解

Abstract:

Using tin tetrachloride pentahydrate, ethylene glycol and ammonia as raw materials, tin oxide nanoparticles were rapidly synthesized under microwave-assisted hydrothermal conditions. Urea was used as a precursor to obtain g-C₃N₄ in a muffle furnace. Hydrocarbon-synthesized carbon quantum dots were prepared from citric acid and ethylenediamine, and finally stirred in a fume hood to obtain carbon quantum dot-loaded carbon nitride/tin oxide composites. TEM, X-ray diffraction (XRD), nitrogen adsorption-desorption isotherm (BET), ultraviolet-visible spectrophotometer (UV-vis) and electron spin (paramagnetic) resonance spectrometer (ESR) were used to characterize the morphology, structural characteristics, absorbance of the composite and characterization and analysis of active substances in the process of photocatalysis. The photocatalytic performance of the samples was tested by degrading rhodamine B (RhB) under ultraviolet light. The experimental results found the red shift of the absorption edge of the ultraviolet-visible spectroscopic spectrum, indicating that the loaded carbon quantum dots can improve the response of the composite in the visible light region. The photocatalytic experiments showed that the loaded carbon quantum dots can improve the photocatalysis of the g-C₃N₄/SnO₂ composite performance. When the load of carbon quantum dots was 7%, the degradation efficiency of composites was the highest and the degradation efficiency of RhB under 3h was 97%. In addition, the microwave-assisted hydrothermal method can synthesize a large amount of tin oxide nanoparticles in a short time and the tin oxide nanoparticles had a small grain size (8.5nm), which can be efficiently prepared and applied in the field of environmental protection.

Key words: carbon quantum dots, g-C₃N₄/SnO₂, composites, photocatalytic, degradation

中图分类号:

X522

何源, 许磊, 夏仡, 王学谦, 刚瑞奇, 王郎郎. 碳量子点修饰g-C₃N₄/SnO₂复合材料光催化性能[J]. 化工进展, 2021, 40(2): 908-916.

Yuan HE, Lei XU, Yi XIA, Xueqian WANG, Ruiqi GANG, Langlang WANG. Photocatalytic performance of carbon quantum dots modified g-C₃N₄/SnO₂ composites[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 908-916.

图/表 9

图1 碳量子点（CQDs）与负载CQDs（7%）的g-C3N4/SnO2复合材料的透射电子显微镜图

图2 负载不同碳量子点含量的g-C3N4/SnO2复合材料的XRD图

图3 负载不同碳量子点含量的g-C3N4/SnO2复合材料的比表面积和孔径分布

图4 负载不同含量碳量子点g-C3N4/SnO2复合材料的紫外-可见漫反射吸收谱图

图5 g-C3N4/SnO2复合材料光催化降解罗丹明B

图6 活性物种捕获试验

图7 电子自旋共振图

图8 光催化机理

图9 GS/CQDs-7%复合材料的稳定性

参考文献 28

1	LIU Yushan, LI Wei, WU Peng, et al. Preparation and applications of carbon quantum dots prepared via hydrothermal carbonization method[J]. Progress in Chemistry, 2018, 30(4): 349-364.
2	SHANG Wangji, CAI Tao, ZHANG Yunxiao, et al. Facile one pot pyrolysis synthesis of carbon quantum dots and graphene oxide nanomaterials: all carbon hybrids as eco-environmental lubricants for low friction and remarkable wear-resistance[J]. Tribology International, 2018, 118: 373-380.
3	LIU Yang, JIAO Yang, ZHANG Zhenglin, et al. Hierarchical SnO₂ nanostructures made of intermingled ultrathin nanosheets for environmental remediation, smart gas sensor, and supercapacitor applications[J]. ACS Applied Materials & Interfaces, 2014, 6(3): 2174-2184.
4	RAMASAMY E, Jinwoo LEE. Ordered mesoporous SnO₂-based photoanodes for high-performance dye-sensitized solar cells[J]. The Journal of Physical Chemistry C, 2010, 114(50): 22032-22037.
5	DONG Fan, WU Liwen, SUN Yanjuan, et al. Efficient synthesis of polymeric g-C₃N₄ layered materials as novel efficient visible light driven photocatalysts[J]. Journal of Materials Chemistry, 2011, 21: 15171-15174.
6	ZHANG Zhenzong, PAN Ziwei, GUO Yongfu, et al. In-situ growth of all-solid Z-scheme heterojunction photocatalyst of Bi₇O₉I₃/g-C₃N₄ and high efficient degradation of antibiotic under visible light[J]. Applied Catalysis B: Environmental, 2020, 261: 118212.
7	SEZA A, SOLEIMANI F, NASERI N, et al. Novel microwave-assisted synthesis of porous g-C₃N₄/SnO₂ nanocomposite for solar water-splitting[J]. Applied Surface Science, 2018, 440: 153-161.
8	CHEN Yingzhi, LI Wenhao, JIANG Dongjian, et al. Facile synthesis of bimodal macroporous g-C₃N₄/SnO₂ nanohybrids with enhanced photocatalytic activity[J]. Science Bulletin, 2019, 64: 44-53.
9	PENG Fengping, NI Yaru, ZHOU Qiang, et al. New g-C₃N₄ based photocatalytic cement with enhanced visible-light photocatalytic activity by constructing muscovite sheet/SnO₂ structures[J]. Construction and Building Materials, 2018, 179: 315-325.
10	MUTHUSANKAR G, SETHUPATHI M, CHEN Shenming, et al. N-doped carbon quantum dots@hexagonal porous copper oxide decorated multiwall carbon nanotubes: a hybrid composite material for an efficient ultra-sensitive determination of caffeic acid[J]. Composites Part B, 2019, 174: 106973.
11	ZHAO Chun, LIAO Zhenzhu, LIU Wen, et al. Carbon quantum dots modified tubular g-C₃N₄ with enhanced photocatalytic activity for carbamazepine elimination: mechanisms, degradation pathway and DFT calculation[J]. Journal of Hazardous Materials, 2020, 381: 120957.
12	DI Guanglan, ZHU Zhiliang, DAI Qi, et al. Wavelength-dependent effects of carbon quantum dots on the photocatalytic activity of g-C₃N₄ enabled by LEDs[J]. Chemical Engineering Journal, 2020, 379: 122296.
13	ZHU Youqi, LI Chao, CAO Chuanbao. Strongly coupled mesoporous SnO₂-graphene hybrid with enhanced electrochemical and photocatalytic activity[J]. RSC Advances, 2013, 3: 11860-11868.
14	KRISHNAKUMAR T, JAYAPRAKASH R, PARTHIBAVARMAN M, et al. Microwave-assisted synthesis and investigation of SnO₂ nanoparticles[J]. Materials Letters, 2009, 63: 896-898.
15	NARSIMULU D, VINOTH S, SRINADHU E S, et al. Surfactant-free microwave hydrothermal synthesis of SnO₂ nanosheets as an anode material for lithium battery applications[J]. Ceramics International, 2018, 44(1): 201-207.
16	CHEN Yingzhi, LI Wenhao, JIANG Dongjian, et al. Facile synthesis of bimodal macroporous g-C₃N₄/SnO₂ nanohybrids with enhanced photocatalytic activity[J]. Science Bulletin, 2019, 64: 44-53.
17	ZANG Yipeng, LI Liping, LI Xiaoguo, et al. Synergistic collaboration of g-C₃N₄/SnO₂ composites for enhanced visible-light photocatalytic activity[J]. Chemical Engineering Journal, 2014, 246: 277-286.
18	LI Kui, SU Fengyun, ZHANG Weide. Modification of g-C₃N₄ nanosheets by carbon quantum dots for highly efficient photocatalytic generation of hydrogen[J]. Applied Surface Science, 2016, 375: 110-117.
19	WANG Fengliang, WANG Yingfei, FENG Yiping, et al. Novel ternary photocatalyst of single atom-dispersed silver and carbon quantum dots co-loaded with ultrathin g-C₃N₄ for broad spectrum photocatalytic degradation of naproxen[J]. Applied Catalysis B: Environmental, 2018, 221: 510-520.
20	TIAN Na, ZHANG Yihe, LI Xiaowei, et al. Precursor-reforming protocol to 3D mesoporous g-C₃N₄ established by ultrathin self-doped nanosheets for superior hydrogen evolution[J]. Nano Energy, 2017, 38: 72-81.
21	CHU Liangliang, ZHANG Jing, WU Zisheng, et al. Solar-driven photocatalytic removal of organic pollutants over direct Z-scheme coral-branch shape Bi₂O₃/SnO₂ composites[J]. Materials Characterization, 2020, 159: 110036.
22	CAO Jianliang, QIN Cong, WANG Yan. Synthesis of g-C₃N₄ nanosheets decorated flower-like tin oxide composites and their improved ethanol gas sensing properties[J]. Journal of Alloys and Compounds, 2017, 728: 1101-1109.
23	PETR P, LADISLAV S, RICHARD D, et al. Nanocomposites of SnO₂ and g-C₃N₄: preparation, characterization and photocatalysis under visible LED irradiation[J]. Ceramics International, 2018, 44(4): 3837-3846.
24	WANG Fengliang, CHEN Ping, FENG Yiping, et al. Facile synthesis of N-doped carbon dots/g-C₃N₄ photocatalyst with enhanced visible-light photocatalytic activity for the degradation of indomethacin[J]. Applied Catalysis B: Environmental, 2017, 207: 103-113.
25	PREKODRAVAC J, VASILJEVIĆ B, MARKOVIĆ Z, et al. Green and facile microwave assisted synthesis of (metal-free) N-doped carbon quantum dots for catalytic applications[J]. Ceramics International, 2019, 45: 17006-17013.
26	WU Yan, WANG Hou, TU Wenguang, et al. Petal-like CdS nanostructures coated with exfoliated sulfur-doped carbon nitride via chemically activated chain termination for enhanced visible-light-driven photocatalytic water puriﬁcation and H₂ generation[J]. Applied Catalysis B: Environmental, 2018, 229: 181-191.
27	霍朝晖, 杨晓珊, 陈晓丽, 等. 纳米银/二维石墨相氮化碳/还原氧化石墨烯复合材料的制备及其光催化降解抗生素[J]. 应用化学, 2020, 37(4): 471-480.
	HUO Zhaohui, YANG Xiaoshan, CHEN Xiaoli, et al. Preparation of Ag/two-dimensional graphitic carbon nitride/reduced graphene oxide composite and its photocatalytic degradation of antibiotics[J]. Chinese Journal of Applied Chemistry, 2020, 37(4): 471-480.
28	ASADZADEH-KHANEGHAH S, HABIBI-YANGJEH A, VADIVEL S. Fabrication of novel g-C₃N₄ nanosheet/carbon dots/Ag₆Si₂O₇ nanocomposites with high stability and enhanced visible-light photocatalytic activity[J]. Journal of the Taiwan Institute of Chemical Engineers, 2019, 103: 94-109.

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碳量子点修饰g-C₃N₄/SnO₂复合材料光催化性能

Photocatalytic performance of carbon quantum dots modified g-C₃N₄/SnO₂ composites

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