对氨基苯磺酸修饰MoO3/PPy复合材料室温下对氨气的监测

doi:10.15541/jim20240218

无机材料学报 ›› 2024, Vol. 39 ›› Issue (11): 1245-1253.DOI: 10.15541/jim20240218 CSTR: 32189.14.10.15541/jim20240218

对氨基苯磺酸修饰MoO₃/PPy复合材料室温下对氨气的监测

丁宁宁¹^,²(), 孙建华¹^,², 韦旭¹^,², 孙丽霞¹^,²()

1.广西大学化学化工学院, 南宁 530004
2.广西石化资源加工及过程强化技术重点实验室, 南宁 530004

收稿日期:2024-04-26 修回日期:2024-06-24 出版日期:2024-11-20 网络出版日期:2024-07-16
通讯作者: 孙丽霞, 副教授. E-mail: binglin0628@163.com
作者简介:丁宁宁(1997-), 女, 硕士研究生. E-mail: dingning1585@163.com
基金资助:
国家自然科学基金(22165001);国家自然科学基金(52002088);广西自然科学基金(2018GXNSFAA294001)

Monitoring Ammonia at Room Temperature of p-Aminobenzene Sulfonic Acid Modified MoO₃/PPy Composites

DING Ningning¹^,²(), SUN Jianhua¹^,², WEI Xu¹^,², SUN Lixia¹^,²()

1. School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China
2. Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Nanning 530004, China

Received:2024-04-26 Revised:2024-06-24 Published:2024-11-20 Online:2024-07-16
Contact: SUN Lixia, associate professor. E-mail: binglin0628@163.com
About author:DING Ningning (1997-), female, Master candidate. E-mail: dingning1585@163.com
Supported by:
National Natural Science Foundation of China(22165001);National Natural Science Foundation of China(52002088);Guangxi Natural Science Foundation Project(2018GXNSFAA294001)

摘要/Abstract

摘要：

氨气是一种有害的大气污染物, 对人类健康和生态环境造成严重的危害, 因此开发低能耗、高性能的氨气实时监测系统势在必行。本工作以MoO₃和吡咯单体(Py)为原料, FeCl₃为氧化剂, 对氨基苯磺酸(pABSA)为阴离子表面活性剂, 采用原位化学氧化聚合法制备了pABSA修饰的MoO₃/聚吡咯(PPy)复合材料。通过不同手段对材料的微观结构进行表征, 探究了pABSA修饰对MoO₃/PPy复合材料气敏性能的影响。结果表明: pABSA-MoO₃/PPy复合材料在室温下对质量浓度1×10⁵ µg/L氨气的响应值为188%, 为纯PPy(22%)的~8倍, 并且表现出优异的选择性和稳定性。气敏性能提升归因于MoO₃与PPy之间形成的异质结以及pABSA的修饰使材料表面载流子增多。

关键词: 聚吡咯, MoO₃, 对氨基苯磺酸, 氨气, 气敏性能, 电荷传输

Abstract:

Ammonia is a harmful atmospheric pollutant that poses serious threats to human health and ecological environment. Therefore, the development of low-energy, high-performance and real-time ammonia monitoring system is imperative. In this study, p-aminobenzene sulfonic acid (pABSA) modified MoO₃/polypyrrole (PPy) composite materials were successfully prepared using an in situ chemical oxidation polymerization method with MoO₃ and pyrrole monomer (Py) as raw materials and FeCl₃ as an oxidant, along with pABSA as an anionic surfactant. Microstructure of the materials was characterized to explore influence of pABSA-modified MoO₃/PPy composite materials on the gas sensing performance. The results demonstrate that at room temperature, the response value of pABSA-modified MoO₃/PPy composite material to a mass concentration of 1×10⁵ µg/L ammonia is 188%, which is ~8 times higher than that of pure PPy (22%), exhibiting excellent selectivity and stability. The enhancement in sensing performance can be attributed to the formation of a heterojunction between MoO₃ and PPy as well as surface modification by pABSA leading to increased mobile charge carriers on the material's surface.

Key words: polypyrrole, MoO₃, p-aminobenzene sulfonic acid, ammonia, gas sensitivity, charge transport

中图分类号:

TB332

丁宁宁, 孙建华, 韦旭, 孙丽霞. 对氨基苯磺酸修饰MoO₃/PPy复合材料室温下对氨气的监测[J]. 无机材料学报, 2024, 39(11): 1245-1253.

DING Ningning, SUN Jianhua, WEI Xu, SUN Lixia. Monitoring Ammonia at Room Temperature of p-Aminobenzene Sulfonic Acid Modified MoO₃/PPy Composites[J]. Journal of Inorganic Materials, 2024, 39(11): 1245-1253.

图/表 13

图1 样品的XRD谱图

Fig. 1 XRD patterns of samples

图2 样品的FT-IR图谱

Fig. 2 FT-IR spectra of samples

图3 样品的拉曼光谱图

Fig. 3 Raman spectra of samples

图4 样品的电镜图和面元素扫描图

Fig. 4 Electron microscopy and surface element scanning of samples (a-d) SEM images of (a) MoO3, (b) PPy, (c) MP10 and (d) MPA40; (e) TEM and (f) HRTEM images of MPA40; (g-l) Element mappings of MPA40

表1 材料的Zeta电位值

Table 1 Zeta potential of the materials

Sample	Zeta potential/mV
PPy	-13
MP10	-18
MPA20	-25
MPA30	-27
MPA40	-33
MPA50	-30
MPA60	-30

图5 样品的电学性能测试

Fig. 5 Electrical properties tests of samples (a) EIS plots of PPy, MP10 and MPA40; (b) Mott-Schottky plots of MoO3 and MPA40; Colorful figures are available on website

图6 PPy、MP10和MPA40的XPS光谱图

Fig. 6 XPS spectra of PPy, MP10, and MPA40 (a) N1s and (b) O1s of PPy, MP10, and MPA40; (c) S2p of MPA40

图7 室温下样品对1×105 µg/L NH3的灵敏度

Fig. 7 Sensitivity of samples to 1×105 µg/L NH3 at room temperature

图8 PPy、MP10和MPA40在室温下对不同目标气体的灵敏度

Fig. 8 Sensitivity of PPy, MP10 and MPA40 to different target gases at room temperature

图9 纯PPy、MP10、MPA40对不同浓度水平氨气的(a)暂态响应和(b)线性拟合曲线

Fig. 9 (a) Transient response and (b) linear fitting curves of pure PPy, MP10 and MPA40 to different concentration levels of ammonia

图10 样品对1×105 µg/L氨气的(a)重复性和(b)长期稳定性测试

Fig. 10 (a) Repeatability and (b) long-term stability tests of samples for 1×105 µg/L ammonia

表2 不同材料对氨气的气敏性能比较

Table 2 Ammonia sensing properties of different materials

Material	T/℃	Mass concentration/ (µg·L^-1)	Response/%	Ref.
PPy	RT	1×10⁵	34.7	[43]
PPy-V₂O₅-MnO₂	RT	0.2×10⁵	45.67	[44]
MXene/MoS₂/PPy	RT	0.1×10⁵	108	[45]
PPy/CeO₂	RT	50×10⁵	93.4	[46]
NiO/PPy	RT	45	65	[47]
rGO-PPy-SnO₂	RT	0.1×10⁵	53	[48]
PPy-ZnO-CSA	RT	1.2×10⁵	79	[15]
pABSA-MoO₃/PPy	RT	1×10⁵	188	This work

图11 pABSA-MoO3/PPy复合材料气敏机理示意图

Fig. 11 Schematic diagram of gas sensing mechanism of pABSA-MoO3/PPy composites

参考文献 50

[1]	GUPTA V, MALIK R, KUMAR L. Highly efficient and cost- effective polyaniline-based ammonia sensor on the biodegradable paper substrate at room temperature. Materials Chemistry and Physics, 2023, 310: 128388.
[2]	LI P P, WANG B, QIN C, et al. Band-gap-tunable CeO₂ nanoparticles for room-temperature NH₃ gas sensors. Ceramics International, 2020, 46(11): 19232.
[3]	KWAK D, LEI Y, MARIC R. Ammonia gas sensors: a comprehensive review. Talanta, 2019, 204: 713. DOI PMID
[4]	YUAN K P, ZHU L Y, YANG J H, et al. Precise preparation of WO₃@SnO₂ core shell nanosheets for efficient NH₃ gas sensing. Journal of Colloid and Interface Science, 2020, 568: 81.
[5]	GAUTAM S K, PANDA S. Highly sensitive Cu-ethylenediamine/ PANI composite sensor for NH₃ detection at room temperature. Talanta, 2023, 258: 124418.
[6]	NAKATE U T, BHUYAN P, YU Y T, et al. Synthesis and characterizations of highly responsive H₂S sensor using p-type Co₃O₄ nanoparticles/nanorods mixed nanostructures. International Journal of Hydrogen Energy, 2022, 47(12): 8145.
[7]	WEN X H, SUN J H, SUN L X, et al. Preparation and acetone sensing properties of CuO-CeO₂ nanocomposites with p-n heterostructures. Fine Chemistry, 2021, 38(4): 736.
[8]	ANANDA S R, KUMARI L, MURUGENDRAPPA M V. Studies on room-temperature acetone sensing properties of ZnCo₂O₄/PPy and MnCo₂O₄/PPy nanocomposites for diabetes diagnosis. Applied Physics A, 2022, 128(8): 669.
[9]	SETKA M, CALAVIA R, VOJKUVKA L, et al. Raman and XPS studies of ammonia sensitive polypyrrole nanorods and nanoparticles. Scientific Reports, 2019, 9: 8465. DOI PMID
[10]	GAO L, YIN C Q, LUO Y Y, et al. Facile synthesis of the composites of polyaniline and TiO₂ nanoparticles using self-assembly method and their application in gas sensing. Nanomaterials, 2019, 9(4): 493.
[11]	SETKA M, BAHOS F A, MATATAGUI D, et al. Love wave sensors based on gold nanoparticle-modified polypyrrole and their properties to ammonia and ethylene. Sensors and Actuators B: Chemical, 2020, 304: 127337.
[12]	SOOD Y, PAWAR V S, MUDILA H, et al. A review on synthetic strategies and gas sensing approach for polypyrrole-based hybrid nanocomposites. Polymer Engineering and Science, 2021, 61(12): 2949.
[13]	ZHANG D Z, WU Z L, ZONG X Q, et al. Fabrication of polypyrrole/ Zn₂SnO₄ nanofilm for ultra-highly sensitive ammonia sensing application. Sensors and Actuators B: Chemical, 2018, 274: 575.
[14]	KAUR A, KUMAR R. Sensing of ammonia at room temperature by polypyrrole-tin oxide nanostructures: investigation by Kelvin probe force microscopy. Sensors and Actuators A: Physical, 2016, 245: 113.
[15]	JAIN S, KARMAKAR N, SHAH A, et al. Ammonia detection of 1-D ZnO/polypyrrole nanocomposite: effect of CSA doping and their structural, chemical, thermal and gas sensing behavior. Applied Surface Science, 2017, 396: 1317.
[16]	MA Y Z, ZHANG S, WANG Q, et al. Ag-decorated MoO₃ microspheres gas sensor for triethylamine detection with rapid response/recovery. Inorganic Chemistry Communications, 2023, 157: 111442.
[17]	WANG C, YANG M, LIU L H, et al. One-step synthesis of polypyrrole/Fe₂O₃ nanocomposite and the enhanced response of NO₂ at low temperature. Journal of Colloid and Interface Science, 2020, 560: 312.
[18]	MANE A T, NAVALE S T, PATIL V B. Room temperature NO₂ gas sensing properties of DBSA doped PPy-WO₃ hybrid nanocomposite sensor. Organic Electronics, 2015, 19: 15.
[19]	SOBHANI-NASAB A, BEHVANDI S, KARIMI M A, et al. Synergetic effect of graphene oxide and C₃N₄ as co-catalyst for enhanced photocatalytic performance of dyes on Yb₂(MoO₄)₃/ YbMoO₄ nanocomposite. Ceramics International, 2019, 45(14): 17847.
[20]	NEISI Z, ANSARI-ASL Z, JAFARINEJAD-FARSANGI S, et al. Synthesis, characterization and biocompatibility of polypyrrole/ Cu(II) metal-organic framework nanocomposites. Colloids and Surfaces B: Biointerfaces, 2019, 178: 365.
[21]	ZHOU K F, SHEN D F, LI X, et al. Molybdenum oxide-based metal-organic framework/polypyrrole nanocomposites for enhancing electrochemical detection of dopamine. Talanta, 2020, 209: 120507.
[22]	NALAGE S R, NAVALE S T, MANE R S, et al. Preparation of camphor-sulfonic acid doped PPy-NiO hybrid nanocomposite for detection of toxic nitrogen dioxide. Synthetic Metals, 2015, 209: 426.
[23]	DUONG N H, NGUYEN T T, TRAN D V, et al. Synergistic effects in the gas sensitivity of polypyrrole/single wall carbon nanotube composites. Sensors, 2012, 12(6): 7965. DOI PMID
[24]	IDRIS N H, WANG J Z, CHOU S L, et al. Effects of polypyrrole on the performance of nickel oxide anode materials for rechargeable lithium-ion batteries. Journal of Materials Research, 2011, 26(7): 860.
[25]	JIAO Y, CHEN G, CHEN D H, et al. Bimetal-organic framework assisted polymerization of pyrrole involving air oxidant to prepare composite electrodes for portable energy storage. Journal of Materials Chemistry A, 2017, 5(45): 23744.
[26]	ZAKHAROVA G S, SCHMIDT C, OTTMANN A, et al. Microwave-assisted hydrothermal synthesis and electrochemical studies of α- and h-MoO₃. Journal of Solid State Electrochemistry, 2018, 22(12): 3651.
[27]	RAUT B T, CHOUGULE M A, GHANWAT A A, et al. Polyaniline-CdS nanocomposites: effect of camphor sulfonic acid doping on structural, microstructural, optical and electrical properties. Journal of Materials Science-Materials in Electronics, 2012, 23(12): 2104.
[28]	WEI Z Q, HOU S, LIN X, et al. Unexpected boosted solar water oxidation by nonconjugated polymer-mediated tandem charge transfer. Journal of the American Chemical Society, 2020, 142(52): 21899.
[29]	YU W L, LI F, HUANG T, et al. Go beyond the limit: rationally designed mixed-dimensional perovskite/semiconductor heterostructures and their applications. Innovation, 2023, 4(1): 100363.
[30]	HAN Z Z, WANG J J, LIAO L, et al. Phosphorus doped TiO₂ as oxygen sensor with low operating temperature and sensing mechanism. Applied Surface Science, 2013, 273: 349.
[31]	HONGSITH N, CHANSURIYA S, KOENROBKET S, et al. Investigating of transition state on the Pd-Au decorated ZnO nanoparticle layers for gas sensor application. Heliyon, 2023, 9(9): 19402.
[32]	CHANG J N, ZHANG H J, CAO J L, et al. Ultrahigh sensitive and selective triethylamine sensor based on h-BN modified MoO₃ nanowires. Advanced Powder Technology, 2022, 33(2): 103432.
[33]	IKRAM M, LIU L J, LV H, et al. Intercalation of Bi₂O₃/Bi₂S₃ nanoparticles into highly expanded MoS₂ nanosheets for greatly enhanced gas sensing performance at room temperature. Journal of Hazardous Materials, 2019, 363: 335.
[34]	YU J G, YUE L, LIU S W, et al. Hydrothermal preparation and photocatalytic activity of mesoporous Au-TiO₂ nanocomposite microspheres. Journal of Colloid and Interface Science, 2009, 334(1): 58.
[35]	ZHAO H Y, SUN J H, LIU J M, et al. UV-triggered carrier transport regulation of fibrous NiO/SnO₂ heterostructures for triethylamine detection. Chemical Engineering Journal, 2023, 476: 146687.
[36]	LI X, SUN L J, YANG X Y, et al. Enhancing the colorimetric detection of H₂O₂ and ascorbic acid on polypyrrole coated fluconazole-functionalized POMOFs. Analyst, 2019, 144(10): 3347.
[37]	ZHANG J, WU C Y, LI T, et al. Highly sensitive and ultralow detection limit of room-temperature NO₂ sensors using in-situ growth of PPy on mesoporous NiO nanosheets. Organic Electronics, 2020, 77: 105504.
[38]	QIAO T T, WANG G S, SHEN Y B, et al. Rational design of CuO/In₂O₃ heterostructures with flower-like structures for low temperature detection of formaldehyde. Journal of Alloys and Compounds, 2022, 896: 16959.
[39]	LIU J Y, DAI M J, WANG T S, et al. Enhanced gas sensing properties of SnO₂ hollow spheres decorated with CeO₂ nanoparticles heterostructure composite materials. ACS Applied Materials & Interfaces, 2016, 8(10): 6669.
[40]	ANDREOLI E, ROONEY D A, REDINGTON W, et al. Electrochemical deposition of hierarchical micro/nanostructures of copper hydroxysulfates on polypyrrole-polystyrene sulfonate films. Journal of Physical Chemistry C, 2011, 115(17): 8725.
[41]	KARMAKAR N, FERNANDES R, JAIN S, et al. Room temperature NO₂ gas sensing properties of p-toluenesulfonic acid doped silver-polypyrrole nanocomposite. Sensors and Actuators B: Chemical, 2017, 242: 118.
[42]	XU L, GE M Y, ZHANG F, et al. Nanostructured of SnO₂/NiO composite as a highly selective formaldehyde gas sensor. Journal of Materials Research, 2020, 35(22): 3079.
[43]	LAWANIYA S D, KUMAR S, YU Y, et al. Ammonia sensing properties of PPy nanostructures (urchins/flowers) towards low-cost and flexible gas sensors at room temperature. Sensors and Actuators B: Chemical, 2023, 382: 133566.
[44]	MALOOK K, KHAN H, SHAH M. Ammonia sensing behavior of polypyrrole-bimetallic oxide composites. Polymer Composites, 2020, 41(7): 2610.
[45]	LU L, LIU M Y, SUI Q L, et al. MXene/MoS₂ nanosheet/ polypyrrole for high-sensitivity detection of ammonia gas at room temperature. Materials Today Communications, 2023, 35: 106239.
[46]	HUSAIN A, AL-ZAHRANI S A, AL OTAIBI A, et al. Fabrication of reproducible and selective ammonia vapor sensor-pellet of polypyrrole/cerium oxide nanocomposite for prompt detection at room temperature. Polymers, 2021, 13(11): 1829.
[47]	HIEN H T, THU D T A, NGAN P Q, et al. High NH₃ sensing performance of NiO/PPy hybrid nanostructures. Sensors and Actuators B: Chemical, 2021, 340: 129986.
[48]	AMITH S L, GURUNATHAN K. Active sites tailored rGO-PPy nanosheets with high crystalline tetragonal SnO₂ nanocrystals for ammonia e-sensitization at room temperature. Journal of Alloys and Compounds, 2023, 960: 170819.
[49]	SHEN C Y, HUNG T T, CHUANG Y W, et al. Room-temperature NH₃ gas surface acoustic wave (SAW) sensors based on graphene/PPy composite films decorated by Au nanoparticles with ppb detection ability. Polymers, 2023, 15(22): 4353.
[50]	PATOWARY B B, LASKAR S, NARZARY R, et al. Synthesis, characterization, and study of NO₂ gas sensing behavior of CSA doped PANi-Ta₂O₅ nanocomposite. IEEE Sensors Journal, 2020, 20(7): 3429.

对氨基苯磺酸修饰MoO₃/PPy复合材料室温下对氨气的监测

Monitoring Ammonia at Room Temperature of p-Aminobenzene Sulfonic Acid Modified MoO₃/PPy Composites

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