Ultrasensitive methyl salicylate gas sensing determined by Pd-doped SnO₂

Abstract

Efficient chemical warfare agents (CWAs) detection is required to protect people from the CWAs in war and terrorism. In this work, a Pd-doped SnO₂ nanoparticles-based gas sensor was developed to detect a nerve agent simulant named methyl salicylate. The sensing measurements of methyl salicylate under different Pd doping amounts found that the 0.5 at.% Pd-doped SnO₂ exhibited a significant improvement in the detection of methyl salicylate at the ppb (1 ppb = 10⁻⁹) level, and the response value to 160 ppb methyl salicylate is 0.72 at 250 °C. Compared with the pure SnO₂, the response value is increased by 4.5 times, which could be attributed to the influence of the noble metal Pd on the oxygen state and its catalytic effect. In addition, the 0.5 at.% Pd-doped SnO₂ sensor still has an obvious response to 16 ppb methyl salicylate with a response value of 0.13, indicating the lower detection limit of the sensor.

Graphical abstract

Keywords

SnO₂ / methyl salicylate / gas sensor / Pd doping / noble metal

References

[1] Costanzi S, Machado J H, Mitchell M . Nerve agents: what they are, how they work, how to counter them.ACS Chemical Neuroscience, 2018, 9(5): 873–885

[2] Franca T C C, Kitagawa D A S, Cavalcante S F A, . Novichoks: the dangerous fourth generation of chemical weapons.International Journal of Molecular Sciences, 2019, 20(5): 1222

[3] Yang L, Taylor R, de Jong W A, . A model DMMP/TiO₂ (1 1 0) intermolecular potential energy function developed from ab initio calculations.The Journal of Physical Chemistry C, 2011, 115(25): 12403–12413

[4] Chen D, Zhang K, Zhou H, . A wireless-electrodeless quartz crystal microbalance with dissipation DMMP sensor.Sensors and Actuators B: Chemical, 2018, 261: 408–417

[5] Yoo J, Kim D, Yang H, . Olfactory receptor-based CNT-FET sensor for the detection of DMMP as a simulant of sarin.Sensors and Actuators B: Chemical, 2022, 354: 131188

[6] Heo G, Manivannan R, Kim H, . Liquid and gaseous state visual detection of chemical warfare agent mimic DCP by optical sensor.Dyes and Pigments, 2019, 171: 107712

[7] Cai Y C, Li C, Song Q H . Fluorescent chemosensors with varying degrees of intramolecular charge transfer for detection of a nerve agent mimic in solutions and in vapor.ACS Sensors, 2017, 2(6): 834–841

[8] Yang Z, Zhang Y, Zhao L, . The synergistic effects of oxygen vacancy engineering and surface gold decoration on commercial SnO₂ for ppb-level DMMP sensing.Journal of Colloid and Interface Science, 2022, 608: 2703–2717

[9] Chauhan S, Chauhan S, D’Cruz R, . Chemical warfare agents.Environmental Toxicology and Pharmacology, 2008, 26(2): 113–122

[10] Wild A, Winter A, Hager M D, . Fluorometric, water-based sensors for the detection of nerve gas G mimics DMMP, DCP and DCNP.Chemical Communications, 2012, 48(7): 964–966

[11] Lu D, Shao G, Du D, . Enzyme entrapped nanoporous scaffolds formed through flow-induced gelation in a microfluidic filter device for sensitive biosensing of organophosphorus compounds.Lab on a Chip, 2011, 11(3): 381–384

[12] Fan S, Zhang G, Dennison G H, . Challenges in fluorescence detection of chemical warfare agent vapors using solid-state films.Advanced Materials, 2020, 32(18): 1905785

[13] Dai Z, Duan G, Cheng Z, . Janus gas: reversible redox transition of Sarin enables its selective detection by an ethanol modified nanoporous SnO₂ chemiresistor.Chemical Communications, 2015, 51(38): 8193–8196

[14] Yu C, Hao Q, Saha S, . Integration of metal oxide nanobelts with microsystems for nerve agent detection.Applied Physics Letters, 2005, 86(6): 063101

[15] Yoo R, Yoo S, Lee D, . Highly selective detection of dimethyl methylphosphonate (DMMP) using CuO nanoparticles/ZnO flowers heterojunction.Sensors and Actuators B: Chemical, 2017, 240: 1099–1105

[16] Kim H C, Hong S H, Kim S J, . Effects of additives on the DMMP sensing behavior of SnO₂ nanoparticles synthesized by hydrothermal method.Journal of Sensor Science and Technology, 2011, 20(5): 294–299

[17] Liu L, Liu S . Oxygen vacancies as an efficient strategy for promotion of low concentration SO₂ gas sensing: the case of Au-modified SnO₂.ACS Sustainable Chemistry & Engineering, 2018, 6(10): 13427–13434

[18] Ren H, Zhao W, Wang L, . Preparation of porous flower-like SnO₂ micro/nano structures and their enhanced gas sensing property.Journal of Alloys and Compounds, 2015, 653: 611–618

[19] Kakoty P, Bhuyan M, Das K . Performance of Pd doped SnO₂ as sensing material for tea aromatic chemicals.IEEE Sensors Journal, 2018, 18(11): 4392–4398

[20] Liu X, Chen N, Han B, . Nanoparticle cluster gas sensor: Pt activated SnO₂ nanoparticles for NH₃ detection with ultrahigh sensitivity.Nanoscale, 2015, 7(36): 14872–14880

[21] Jang J-S, Kim S-J, Choi S-J, . Thin-walled SnO₂ nanotubes functionalized with Pt and Au catalysts via the protein templating route and their selective detection of acetone and hydrogen sulfide molecules.Nanoscale, 2015, 7(39): 16417–16426

[22] Xue M, Li F, Chen D, . High-oriented polypyrrole nanotubes for next-generation gas sensor.Advanced Materials, 2016, 28(37): 8265–8270

[23] Ogel E, Müller S A, Sackmann A, . Comparison of the catalytic performance and carbon monoxide sensing behavior of Pd–SnO₂ core@shell nanocomposites.ChemCatChem, 2017, 9(3): 407–413

[24] Tofighi G, Degler D, Junker B, . Microfluidically synthesized Au, Pd and AuPd nanoparticles supported on SnO₂ for gas sensing applications.Sensors and Actuators B: Chemical, 2019, 292: 48–56

[25] Wang M, Lian T, Wang J, . In-situ deposition and subsequent growth of Pd on SnO₂ as catalysts for formate oxidation with excellent Pd utilization and anti-poisoning performance.International Journal of Hydrogen Energy, 2019, 44(39): 21518–21526

[26] Mu J, Chen B, Zhang M, . Enhancement of the visible-light photocatalytic activity of In₂O₃–TiO₂ nanofiber heteroarchitectures.ACS Applied Materials & Interfaces, 2012, 4(1): 424–430

[27] Wang Y, Mu Q, Wang G, . Sensing characterization to NH₃ of nanocrystalline Sb-doped SnO₂ synthesized by a nonaqueous sol–gel route.Sensors and Actuators B: Chemical, 2010, 145(2): 847–853

[28] Correa-Baena J P, Artyushkova K, Santoro C, . Morphological characterization of ALD and doping effects on mesoporous SnO₂ aerogels by XPS and quantitative SEM image analysis.ACS Applied Materials & Interfaces, 2016, 8(15): 9849–9854

[29] Kandasamy M, Seetharaman A, Sivasubramanian D, . Ni-doped SnO₂ nanoparticles for sensing and photocatalysis.ACS Applied Nano Materials, 2018, 1(10): 5823–5836

[30] Ahmed A, Siddique M N, Ali T, . Defect assisted improved room temperature ferromagnetism in Ce doped SnO₂ nanoparticles.Applied Surface Science, 2019, 483: 463–471

[31] Somacescu S, Ghica C, Simion C E, . Nanoclustered Pd decorated nanocrystalline Zn doped SnO₂ for ppb NO₂ detection at low temperature.Sensors and Actuators B: Chemical, 2019, 294: 148–156

[32] Cai Z, Park S . Synthesis of Pd nanoparticle-decorated SnO₂ nanowires and determination of the optimum quantity of Pd nanoparticles for highly sensitive and selective hydrogen gas sensor.Sensors and Actuators B: Chemical, 2020, 322: 128651

[33] Mirzaei A, Leonardi S G, Neri G . Detection of hazardous volatile organic compounds (VOCs) by metal oxide nanostructures-based gas sensors: a review.Ceramics International, 2016, 42(14): 15119–15141

[34] Wang C, Zhang Y, Sun X, . Preparation of Pd/PdO loaded WO₃ microspheres for H₂S detection.Sensors and Actuators B: Chemical, 2020, 321: 128629

[35] Zhou Q, Chen W, Xu L, . Highly sensitive carbon monoxide (CO) gas sensors based on Ni and Zn doped SnO₂ nanomaterials.Ceramics International, 2018, 44(4): 4392–4399

[36] Li G, Wang X, Yan L, . PdPt bimetal-functionalized SnO₂ nanosheets: controllable synthesis and its dual selectivity for detection of carbon monoxide and methane.ACS Applied Materials & Interfaces, 2019, 11(29): 26116–26126

[37] Mirzaei A, Neri G . Microwave-assisted synthesis of metal oxide nanostructures for gas sensing application: a review.Sensors and Actuators B: Chemical, 2016, 237: 749–775

[38] Zhang Y H, Yue L J, Gong F L, . Highly enhanced H₂S gas sensing and magnetic performances of metal doped hexagonal ZnO monolayer.Vacuum, 2017, 141: 109–115

[39] Vallejos S, Stoycheva T, Annanouch F E, . Microsensors based on Pt–nanoparticle functionalised tungsten oxide nanoneedles for monitoring hydrogen sulfide.RSC Advances, 2014, 4(3): 1489–1495

[40] Kim H, Jin C, Park S, . H₂S gas sensing properties of bare and Pd-functionalized CuO nanorods.Sensors and Actuators B: Chemical, 2012, 161(1): 594–599

[41] Sun Y-P, Zhao Y-F, Sun H, . Synthesis and room-temperature H₂S sensing of Pt nanoparticle-functionalized SnO₂ mesoporous nanoflowers.Journal of Alloys and Compounds, 2020, 842: 155813

Disclosure of potential conflicts of interests

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was supported by the Science and Technology on Aerospace Chemical Power Laboratory, Hubei Institute of Aerospace Chemical Technology (U20B2018), the Open Research Fund Program of Science and Technology on Aerospace Chemical Power Laboratory (STACPL320201B02 and STACPL320181B03-1), and the National Natural Science Foundation of China (Nos. 61971204 and 51902114). The authors are very grateful to the technology support by the Analytic Testing Center of Huazhong University of Science and Technology for SEM, TEM and XPS, and the State Key Laboratory of Materials Processing and Die & Mould Technology of Huazhong University of Science and Technology for XRD measurements.

RIGHTS & PERMISSIONS

2022 Higher Education Press