N-Bi2O2CO3/CdSe量子点光催化氧化NO及原位红外光谱研究

doi:10.15541/jim20180299

无机材料学报 ›› 2019, Vol. 34 ›› Issue (4): 425-432.DOI: 10.15541/jim20180299

所属专题：光催化材料与技术；优秀作者论文集锦； 2019~2020年度优秀作者作品欣赏:环境材料

N-Bi₂O₂CO₃/CdSe量子点光催化氧化NO及原位红外光谱研究

刘旸¹,于姗¹(),郑凯文¹,陈维维¹,董兴安²,董帆²,周莹¹()

^1. 西南石油大学材料科学与工程学院, 新能源材料及技术研究中心, 成都 610500
^2. 重庆工商大学环境与资源学院, 催化与环境新材料重庆市重点实验室, 重庆 400067

收稿日期:2018-07-02 修回日期:2018-10-08 出版日期:2019-04-20 网络出版日期:2019-04-15
作者简介:刘旸(1992-), 男, 博士研究生. E-mail:18251856797@163.com
基金资助:
四川省杰出青年科技基金(2014JQ0017);四川省青年科技创新研究团队(2016TD0011)

NO Photo-oxidation and In-situ DRIFTS Studies on N-doped Bi₂O₂CO₃/CdSe Quantum Dot Composite

Yang LIU¹,Shan YU¹(),Kai-Wen ZHENG¹,Wei-Wei CHEN¹,Xing-An DONG²,Fan DONG²,Ying ZHOU¹()

^1. The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, China
^2. Chongqing Key Laboratory Catalysis and New Environmental Materials, College of Environment and Resources, Chongqing Technology and Business University, Chongqing 400067, China

Received:2018-07-02 Revised:2018-10-08 Published:2019-04-20 Online:2019-04-15
Supported by:
Sichuan Youth Science and Technology Foundation(2014JQ0017);Innovative Research Team of Sichuan Province(2016TD0011)

摘要/Abstract

摘要：

本实验成功制备了氮掺杂碳酸氧铋(N-Bi₂O₂CO₃, N-BOC)/硒化镉量子点(CdSe QDs)复合光催化剂, 并将其运用于光催化降解室内空气污染物一氧化氮(NO)。X射线衍射、透射电子显微镜和光电子能谱测试结果表明N-BOC光催化剂在保持原有纳米片结构和形貌的基础上成功负载了CdSe QDs。光催化氧化NO实验结果显示CdSe QDs的引入可显著提高N-BOC的NO去除率, 并且二次毒副产物NO₂生成率大幅度降低至1%, 表明复合光催化剂具有极强的毒副产物抑制特性。固体紫外漫反射吸收光谱和发光光谱测试表明CdSe QDs拓宽并提升了N-BOC的光响应范围和能力, 并有效抑制了光生电子-空穴的复合效率。通过原位漫反射傅里叶变换红外光谱技术(DRIFTS)分析, 发现在N-BOC/CdSe QDs光催化氧化NO反应过程中没有NO₂信号产生, 仅观测到NO₃ ^-相关信号。机理分析表明超氧自由基(O₂ ^-)和光生空穴(h ⁺)是体系中可能存在的活性物种, 实现了对NO到NO₃ ^-的彻底氧化。

关键词: 碳酸氧铋, 硒化镉量子点, 光催化, 一氧化氮, 原位漫反射傅里叶变换红外光谱

Abstract:

Photocatalyst of N-doped Bi₂O₂CO₃ (N-BOC)/CdSe quantun dots (QDs) composite was sucessfully prepared for degradation of nitric oxide (NO), an indoor air pollutant. The results of X-ray diffraction, transmisssion electron microscopy and X-ray photoelectron spectroscopy showed that after combination with CdSe QDs structure and morphology of N-BOC remained the same as before combination. Photocatalytic degradation of NO showed that introduction of CdSe QDs significantly enhanced the removal ratio of NO. Moreover, the generating ratio of toxic byproduct NO₂ decreased to 1%, which indicated efficient inhibition for the toxic byproduct generation. From UV-Vis absorption spectroscopy and photoluminescence spectroscopy, the CdSe QDs showed promotion on light absorption, and inhibition of charged recombination of photo-induced carriers. More importantly, only signals of NO₃ ^- were captured in in situ DRIFTS measurements, whilst the signals from NO₂ could be barely detected during photocatalytic process. Superoxide radicals (O₂ ^-) and holes (h ⁺) are considered to be possible active species in the reaction, which dominate the oxidation process from NO to NO₃ ^-.

Key words: bismuth subcarbonate, cadmium selenide quantum dots, photocatalysis, nitric oxide, in situ DRIFTS

中图分类号:

TQ174

刘旸, 于姗, 郑凯文, 陈维维, 董兴安, 董帆, 周莹. N-Bi₂O₂CO₃/CdSe量子点光催化氧化NO及原位红外光谱研究[J]. 无机材料学报, 2019, 34(4): 425-432.

Yang LIU, Shan YU, Kai-Wen ZHENG, Wei-Wei CHEN, Xing-An DONG, Fan DONG, Ying ZHOU. NO Photo-oxidation and In-situ DRIFTS Studies on N-doped Bi₂O₂CO₃/CdSe Quantum Dot Composite[J]. Journal of Inorganic Materials, 2019, 34(4): 425-432.

图/表 12

图1 光降解NO装置示意图

Fig. 1 Schematic diagram of photo-oxidation NO reaction equipment

图2 可见光下N-BOC和N-BOC/CdSe QDs的NO降解率(a), NO2生成率(b), N-BOC/CdSe QDs (1%)样品的可见光(c)和全光谱下(d)NO循环降解图

Fig. 2 Photocatalytic removal ratio of NO (a) and generation of NO2 (b) in the presence of N-BOC and N-BOC/CdSe QDs under visible light irradiation (λ>420 nm), and photocatalytic recycling tests on N-BOC/CdSe QDs (1%) under visible light (c) and UV-Visible light (d) irradiation

图3 N-BOC和N-BOC/CdSe QDs(1%)的XRD图谱及其相应的N-BOC标准PDF卡片

Fig. 3 XRD patterns of N-BOC and N-BOC/CdSe QDs(1%) and their corresponding standard PDF card

图4 N-BOC/CdSe QDs(1%)的(a) TEM和(b) HRTEM照片

Fig. 4 (a)TEM and (b)HRTEM images of N-BOC/CdSe QDs(1%)

图5 N-BOC和N-BOC/CdSe QDs(1%)的XPS的Bi 4f (a), O 1s (b), C 1s (c)的精细谱和价带谱(d)

Fig. 5 High-resolution XPS spectra of Bi 4f (a), O 1s (b), C 1s (c), and valance band (d) of N-BOC and N-BOC/CdSe QDs (1%) sample

图6 N-BOC和N-BOC/CdSe QDs的紫外-可见漫反射光谱图

Fig. 6 UV-Vis DRS of N-BOC and N-BOC/CdSe QDs Insets are the absorption spectrum of CdSe QDs dispersed in water (up) and enlarged spectra of N-BOC/CdSe QDs composite (down)

图7 N-BOC和N-BOC/CdSe QDs的荧光光谱图

Fig. 7 Photoluminescence spectra of N-BOC and N-BOC/CdSe QDs (1%) Excitation wavelength: 280 nm

表1 不同活性物种的氧化还原电位

Table 1 Redox potentials of different active species

Species	Redox potential (NHE)
Species	Potential/eV	Ref.
O₂/?O₂^-	-0.28	[30]
NO/NO₂	0.94	[29]
NO/NO₃^-	1.03	[29]

图8 N-BOC/CdSe QDs (1%)在暗场吸附(a), 光催化反应(b)和脱附过程中的原位红外光谱图

Fig. 8 In situ DRIFTS of NO adsorption on N-BOC/CdSe QDs (1%) before (a), during (b) and after (c) visible light illumination

表2 NO吸附及光催化过程中关于红外峰的归属

Table 2 Assignments of the IR bands observed during NO adsorption and photocatalysis over N-BOC/CdSe QDs

Wavenumber/cm^-1	Assignment	Ref.
935	Bidentate nitrite	[31]
949, 978	Monodentate nitrate	[32-35]
1002	Bridge nitrate	[32-35]
1024	Bidentate/monodentate nitrate	[8, 32-35]
1092, 1134	NO	[31]
1180	NO^-	[8,18]
1120	Bidentate nitrite	[18, 31]
1262	Monodentate nitrate	[18, 31]

图9 NO吸附以及光催化氧化反应过程示意图

Fig. 9 Proposed processes of NO adsorption and photocatalytic NO oxidation

图10 N-BOC/CdSe QDs光催化氧化NO机理图

Fig. 10 Schematic representation of the mechanism for photodegrading NO by N-BOC/CdSe QDs

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N-Bi₂O₂CO₃/CdSe量子点光催化氧化NO及原位红外光谱研究

NO Photo-oxidation and In-situ DRIFTS Studies on N-doped Bi₂O₂CO₃/CdSe Quantum Dot Composite

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