基于火焰退火多孔CeO2纳米片的环境监测用超快CO气体传感器

doi:10.15541/jim20210142

无机材料学报 ›› 2021, Vol. 36 ›› Issue (11): 1223-1230.DOI: 10.15541/jim20210142

所属专题：【信息功能】敏感陶瓷

基于火焰退火多孔CeO₂纳米片的环境监测用超快CO气体传感器

李鹏鹏(), 王兵(), 王应德()

国防科技大学空天科学学院, 新型陶瓷纤维及其复合材料重点实验室, 长沙 410073

收稿日期:2021-03-10 修回日期:2021-04-10 出版日期:2021-11-20 网络出版日期:2021-04-30
通讯作者: 王应德, 教授. E-mail: wangyingde@nudt.edu.cn;王兵, 副研究员. E-mail: bingwang@nudt.edu.cn
作者简介:李鹏鹏(1995-), 男, 硕士研究生. E-mail: lipengpeng@nudt.edu.cn

Ultrafast CO Sensor Based on Flame-annealed Porous CeO₂ Nanosheets for Environmental Application

LI Pengpeng(), WANG Bing(), WANG Yingde()

Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China

Received:2021-03-10 Revised:2021-04-10 Published:2021-11-20 Online:2021-04-30
Contact: WANG Yingde, professor. E-mail: wangyingde@nudt.edu.cn;WANG Bing, associate professor. E-mail: bingwang@nudt.edu.cn
About author:LI Pengpeng(1995-), male, Master candidate. E-mail: lipengpeng@nudt.edu.cn
Supported by:
National Natural Science Foundation of China(61701514);National Natural Science Foundation of China(51773226);Natural Science Foundation of Hunan Province(2018JJ3603)

摘要/Abstract

摘要：

CO作为一种高毒性的气体,既是污染空气的元凶之一,长时间吸入也会对人体造成极大的伤害,甚至致死。如何实现CO的快速监测是传感领域面临的重要挑战。CO监测对保护人类健康和环境来说是一项必要的工作。在该研究中, 多孔CeO₂纳米片(CeO₂ NSs)通过火焰退火用简单水热法合成的中间产物CeOHCO₃纳米片而得到。通过控制火焰退火时间, 可将氧空位引入到CeO₂纳米片中。结果表明, 退火2 min得到的CeO₂纳米片(CeO₂-2min NSs)对CO气体表现出优异的重复性和选择性。尤其是, CeO₂-2min NSs在450 ℃对500 μL/L CO的相应/恢复时间极快(2 s/2 s), 在宽范围内(10~10000 μL/L) CO浓度与响应值之间存在良好的函数关系。CeO₂-2min NSs优秀的气敏性能可归因于多孔二维结构高的比表面积和晶体内丰富的氧空位。这项工作对设计检测宽范围气体的快响应气体传感器提供了借鉴。

关键词: 火焰退火, 多孔CeO₂纳米片, 氧空位, 气体传感器, 宽范围

Abstract:

As a highly toxic gas, CO is one of the culprits of air pollution. Long-term inhalation will also cause great harm to the human body and even death. How to achieve rapid CO monitoring is an important challenge in sensing field. CO as one of the of air pollution, long time inhalation will reduce the oxygen carrying capacity of blood and in severe cases death. Therefore, effective monitoring of CO is necessary. In this study, porous CeO₂ nanosheets (CeO₂ NSs) were obtained via flame annealing intermediate product CeCO₃OH nanosheets synthesized by simple hydrothermal method. Through controlling of the flame time, oxygen vacancies were introduced into the CeO₂ NSs. As a result, the CeO₂ NSs annealed with 2 min (CeO₂-2min NSs) exhibited outstanding reproducibility and selectivity towards CO gas. Particularly, the response/recovery time were extremely fast (2 s/2 s) towards 500 μL/L CO at 450 ℃ as well as finely functional relationship between response and concentration of CO at a wide detection range (10-10000 μL/L). The superior gas sensing performance of CeO₂-2min NSs can be ascribed to the high aspect ratios of the porous two-dimensional structure and abundant oxygen vacancies in the crystals. This work may supply a strategy for designing ultrafast gas sensors which can detect target gas at a wide range.

Key words: flame annealing, porous CeO₂ nanosheets, oxygen vacancy, gas sensors, wide range

中图分类号:

TQ174

李鹏鹏, 王兵, 王应德. 基于火焰退火多孔CeO₂纳米片的环境监测用超快CO气体传感器[J]. 无机材料学报, 2021, 36(11): 1223-1230.

LI Pengpeng, WANG Bing, WANG Yingde. Ultrafast CO Sensor Based on Flame-annealed Porous CeO₂ Nanosheets for Environmental Application[J]. Journal of Inorganic Materials, 2021, 36(11): 1223-1230.

图/表 14

Fig. 1 Schematic illustration of preparation of CeO2 nanosheets

Fig. 2 XRD patterns of the flame-annealed CeO2 nanosheets

Fig. 3 XPS spectra of the CeO2 NSs (a, b, c) high resolution spectra of O 1s of CeO2-0.5min NSs, CeO2-2min NSs and CeO2-5min NSs; (d, e, f) high resolution spectra of Ce 3d of CeO2-0.5min NSs, CeO2-2min NSs and CeO2-5min NSs

Fig. 4 Morphologies and structure characterizations of the as-prepared samples (a, b, c) TEM images of CeO2-0.5min NSs, CeO2-2min NSs and CeO2-5min NSs (pores are labelled by red dotted circles); (d, e, f) HRTEM images of CeO2-0.5min NSs, CeO2-2min NSs and CeO2-5min NSs

Fig. 5 (a) Nitrogen adsorption-desorption isotherms and (b) pore size distributions of CeO2 NSs

Fig. 6 EPR spectra of CeO2 NSs

Fig. 7 Gas sensing properties of CeO2 NSs (a) Response of CeO2 NSs at different temperatures from 300 ℃ to 500 ℃ with an interval of 50 ℃ towards 500 μL/L CO; (b) Response of CeO2-2min NSs towards 500 μL/L CO at 450 ℃ for seven periods; (c) Transient response of CeO2-2min NSs towards different concentration from 10 μL/L to 10000 μL/L at 450 ℃; (d) Fitting of CO concentration and its corresponding response; (e) Determination of response/recovery time of CeO2-2min NSs towards 500 μL/L CO at 450 ℃; (f) Selectivity of CeO2-2min NSs towards CH4, H2, NH3, NO2 and CO at 450 ℃

Table 1 Recent materials for in CO gas sensing

Material	Concentration/(μL∙L^-1)	Temperature/℃	Sensitivity	(Response/recovery time)/s	Ref.
Co₃O₄ nanostructures	5	100	2.4^a	14/36	[23]
Pd/SnO₂	100	100	3.5^a	60/150	[24]
TiO₂-CeO₂ mixed oxides	400	200	10.7^a	32/45	[25]
SnO₂/MoO₂	100	RT	9.2%^b	20/16	[1]
SnO₂-CeO₂ mixed oxides	500	430	190%^b	26/30	[11]
Pd/SnO₂ nanowires	200	400	6.8^a	5/40	[26]
ZnO nanorods	30	400	1.1^a	46/27	[27]
Porous CeO₂ nanosheets	500	450	12.0%^b	2/2	This work

Fig. 8 Schematic illustration of CO gas sensing mechanism Yellow spheres represent O atoms; Orange spheres represent Ce atoms; Red rings represent the position of oxygen vacancies

Fig. S1 XRD pattern of the intermediate product

Fig. S2 Response of CeO2-2min NSs towards 500 μL/L CO at 450 ℃ under different humidities

Fig. S3 Long-term stability of CeO2-2min NSs towards 500 μL/L CO at 450 ℃ for two weeks

Table S1 Percentage of each element species to the whole element content

	O_S/%	O_V/%	Ce³⁺/%	Ce³⁺/Ce⁴⁺
CeO₂-0.5min NSs	19.0	40.0	26.3	0.357
CeO₂-2min NSs	14.8	43.2	28.6	0.401
CeO₂-5min NSs	15.1	42.7	23.8	0.312

Table S2 Summary of surface area and pore volume of CeO2 NSs

	Surface area/(m²∙g^-1)	Pore volume/ (cm³∙g^-1)	Average pore diameter/nm
CeO₂-0.5min NSs	73.344	0.172	10.1
CeO₂-2min NSs	46.804	0.181	15.5
CeO₂-5min NSs	40.836	0.163	15.8

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基于火焰退火多孔CeO₂纳米片的环境监测用超快CO气体传感器

Ultrafast CO Sensor Based on Flame-annealed Porous CeO₂ Nanosheets for Environmental Application

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