Polypyrrole (PPy) nanorods (NRs) and nanoparticles (NPs) are synthesized via electrochemical and chemical methods, respectively, and tested upon ammonia exposure using Raman and X-ray photoelectron spectroscopy (XPS). Characterization of both nanomaterials via Raman spectroscopy demonstrates the formation of PPy, displaying vibration bands consistent with the literature. Additionally, XPS reveals the presence of neutral PPy species as major components in PPy NRs and PPy NPs, and other species including polarons and bipolarons. Raman and XPS analysis after ammonia exposure show changes in the physical/chemical properties of PPy, confirming the potential of both samples for ammonia sensing. Results demonstrate that the electrochemically synthesized NRs involve both proton and electron transfer mechanisms during ammonia exposure, as opposed to the chemically synthesized NPs, which show a mechanism dominated by electron transfer. Thus, the different detection mechanisms in PPy NRs and PPy NPs appear to be connected to the particular morphological and chemical composition of each film. These results contribute to elucidate the mechanisms involved in ammonia detection and the influence of the synthesis routes and the physical/chemical characteristics of PPy.

Central European Institute of Technology Brno University of Technology Purkyňova 123 612 00 Brno Czech Republic

Department of Microelectronics SIX Research Centre Faculty of Electrical Engineering and Communication Brno University of Technology Technická 3058 10 61600 Brno Czech Republic

Instituto de Microelectrónica de Barcelona Campus UAB Carrer dels Til·lers 08193 Cerdanyola del Vallès Barcelona Spain

Minos Emas Universitat Rovira i Virgili Av Països Catalans 26 43007 Tarragona Spain

Scientific Tecnical Resources Service Universitat Rovira i Virgili Av Països Catalans 26 43007 Tarragona Spain

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Andre RS, et al. Hybrid nanomaterials designed for volatile organic compounds sensors: A review. Materials & Design. 2018;156:154–166. doi: 10.1016/j.matdes.2018.06.041. DOI

Peng G, et al. Diagnosing lung cancer in exhaled breath using gold nanoparticles. Nature Nanotechnology. 2009;4:669–673. doi: 10.1038/nnano.2009.235. PubMed DOI

Sun YF, et al. Metal Oxide Nanostructures and Their Gas Sensing Properties: A Review. Sensors. 2012;12:2610–2631. doi: 10.3390/s120302610. PubMed DOI PMC

Athawale AA, Kulkarni MV. Polyaniline and its substituted derivatives as sensor for aliphatic alcohols. Sensors and Actuators B-Chemical. 2000;67:173–177. doi: 10.1016/s0925-4005(00)00394-4. DOI

Kim J-S, Sohn S-O, Huh J-S. Fabrication and sensing behavior of PVF2 coated-polyaniline sensor for volatile organic compounds. Sensors and Actuators B: Chemical. 2005;108:409–413. doi: 10.1016/j.snb.2004.11.072. DOI

Eaidkong T, et al. Polydiacetylene paper-based colorimetric sensor array for vapor phase detection and identification of volatile organic compounds. Journal of Materials Chemistry. 2012;22:5970–5977. doi: 10.1039/C2JM16273C. DOI

Yoon J, Chae SK, Kim JM. Colorimetric sensors for volatile organic compounds (VOCs) based on conjugated polymer-embedded electrospun fibers. Journal of the American Chemical Society. 2007;129:3038–3039. doi: 10.1021/ja067856+. PubMed DOI

Park E, et al. One-pot synthesis of silver nanoparticles decorated poly(3,4-ethylenedioxythiophene) nanotubes for chemical sensor application. Journal of Materials Chemistry. 2012;22:1521–1526. doi: 10.1039/C1JM13237G. DOI

Guernion N, et al. The fabrication and characterisation of a highly sensitive polypyrrole sensor and its electrical responses to amines of differing basicity at high humidities. Synthetic Metals. 2002;126:301–310. doi: 10.1016/S0379-6779(01)00572-0. DOI

McQuade DT, Pullen AE, Swager TM. Conjugated Polymer-Based Chemical Sensors. Chemical Reviews. 2000;100:2537–2574. doi: 10.1021/cr9801014. PubMed DOI

Šetka Milena, Drbohlavová Jana, Hubálek Jaromír. Nanostructured Polypyrrole-Based Ammonia and Volatile Organic Compound Sensors. Sensors. 2017;17(3):562. doi: 10.3390/s17030562. PubMed DOI PMC

Kwon OS, et al. Resistive Gas Sensors Based on Precisely Size-Controlled Polypyrrole Nanoparticles: Effects of Particle Size and Deposition Method. Journal of Physical Chemistry C. 2010;114:18874–18879. doi: 10.1021/jp1083086. DOI

Hong JY, Yoon H, Jang J. Kinetic Study of the Formation of Polypyrrole Nanoparticles in Water-Soluble Polymer/Metal Cation Systems: A Light-Scattering Analysis. Small. 2010;6:679–686. doi: 10.1002/smll.200902231. PubMed DOI

Hernandez SC, et al. Single polypyrrole nanowire ammonia gas sensor. Electroanalysis. 2007;19:2125–2130. doi: 10.1002/elan.200703933. DOI

Zhang L, et al. A novel ammonia sensor based on high density, small diameter polypyrrole nanowire arrays. Sensors and Actuators B: Chemical. 2009;142:204–209. doi: 10.1016/j.snb.2009.07.042. DOI

Lee J-S, et al. Au-Polypyrrole Framework Nanostructures for Improved Localized Surface Plasmon Resonance Volatile Organic Compounds Gas Sensing. Journal of Nanoscience and Nanotechnology. 2015;15:7738–7742. doi: 10.1166/jnn.2015.11194. PubMed DOI

Joulazadeh M, Navarchian AH. Alcohol Sensibility of One-Dimensional Polyaniline and Polypyrrole Nanostructures. Ieee Sensors Journal. 2015;15:1697–1704. doi: 10.1109/jsen.2014.2360915. DOI

Chartuprayoon N, et al. Wafer-Scale Fabrication of Single Polypyrrole Nanoribbon-Based Ammonia Sensor. Journal of Physical Chemistry C. 2010;114:11103–11108. doi: 10.1021/jp102858w. DOI

Kausaite-Minkstimiene A, Mazeiko V, Ramanaviciene A, Ramanavicius A. Evaluation of chemical synthesis of polypyrrole particles. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2015;483:224–231. doi: 10.1016/j.colsurfa.2015.05.008. DOI

Patois T, et al. Characterization of the surface properties of polypyrrole films: Influence of electrodeposition parameters. Synthetic Metals. 2011;161:2498–2505. doi: 10.1016/j.synthmet.2011.10.003. DOI

Patois T, Lakard B, Martin N, Fievet P. Effect of various parameters on the conductivity of free standing electrosynthesized polypyrrole films. Synthetic Metals. 2010;160:2180–2185. doi: 10.1016/j.synthmet.2010.08.005. DOI

Inzelt G, Pineri M, Schultze JW, Vorotyntsev MA. Electron and proton conducting polymers: recent developments and prospects. Electrochimica Acta. 2000;45:2403–2421. doi: 10.1016/s0013-4686(00)00329-7. DOI

Joshi A, Gangal SA, Gupta SK. Ammonia sensing properties of polypyrrole thin films at room temperature. Sensors and Actuators B: Chemical. 2011;156:938–942. doi: 10.1016/j.snb.2011.03.009. DOI

Santos MJL, Brolo AG, Girotto EM. Study of polaron and bipolaron states in polypyrrole by in situ Raman spectroelectrochemistry. Electrochimica Acta. 2007;52:6141–6145. doi: 10.1016/j.electacta.2007.03.070. DOI

Le TH, Kim Y, Yoon H. Electrical and Electrochemical Properties of Conducting Polymers. Polymers. 2017;9:32. doi: 10.3390/polym9040150. PubMed DOI PMC

Balint R, Cassidy NJ, Cartmell SH. Conductive polymers: Towards a smart biomaterial for tissue engineering. Acta Biomaterialia. 2014;10:2341–2353. doi: 10.1016/j.actbio.2014.02.015. PubMed DOI

Yurtsever M, Yurtsever E. Structural studies of polypyrroles: I. An ab-initio evaluation of bonding through α and β carbons. Synthetic Metals. 1999;98:221–227. doi: 10.1016/S0379-6779(98)00195-7. DOI

Meerholz K, Heinze J. Influence of chain length and defects on the electrical conductivity of conducting polymers. Synthetic Metals. 1993;57:5040–5045. doi: 10.1016/0379-6779(93)90859-U. DOI

Deogaonkar SC, Bhat NV. Polymer based fabrics as transducers in ammonia & ethanol gas sensing. Fiber. Polym. 2015;16:1803–1811. doi: 10.1007/s12221-015-5172-6. DOI

Kharat HJ, et al. Synthesis of polypyrrole films for the development of ammonia sensor. Polymers for Advanced Technologies. 2007;18:397–402. doi: 10.1002/pat.903. DOI

Liu Y-C. Characteristics of vibration modes of polypyrrole on surface-enhanced Raman scattering spectra. Journal of Electroanalytical Chemistry. 2004;571:255–264. doi: 10.1016/j.jelechem.2004.05.015. DOI

Le HNT, Bernard MC, Garcia-Renaud B, Deslouis C. Raman spectroscopy analysis of polypyrrole films as protective coatings on iron. Synthetic Metals. 2004;140:287–293. doi: 10.1016/s0379-6779(03)00376-x. DOI

Gupta S. Hydrogen bubble‐assisted syntheses of polypyrrole micro/nanostructures using electrochemistry: structural and physical property characterization. Journal of Raman Spectroscopy. 2008;39:1343–1355. doi: 10.1002/jrs.2002. DOI

Liu Y-C, Hwang B-J, Jian W-J, Santhanam R. In situ cyclic voltammetry-surface-enhanced Raman spectroscopy: studies on the doping–undoping of polypyrrole film. Thin Solid Films. 2000;374:85–91. doi: 10.1016/S0040-6090(00)01061-0. DOI

Crowley K, Cassidy J. In situ resonance Raman spectroelectrochemistry of polypyrrole doped with dodecylbenzenesulfonate. Journal of Electroanalytical Chemistry. 2003;547:75–82. doi: 10.1016/s0022-0728(03)00191-8. DOI

Xie YB, Du HX. Electrochemical capacitance of a carbon quantum dots-polypyrrole/titania nanotube hybrid. Rsc Advances. 2015;5:89689–89697. doi: 10.1039/c5ra16538e. DOI

Kopecka J, et al. Polypyrrole Nanotubes and Their Carbonized Analogs: Synthesis, Characterization, Gas Sensing Properties. Sensors. 2016;16:13. doi: 10.3390/s16111917. PubMed DOI PMC

Stejskal J, et al. Polypyrrole salts and bases: superior conductivity of nanotubes and their stability towards the loss of conductivity by deprotonation. RSC Advances. 2016;6:88382–88391. doi: 10.1039/c6ra19461c. DOI

Li M, Wei ZX, Jiang L. Polypyrrole nanofiber arrays synthesized by a biphasic electrochemical strategy. Journal of Materials Chemistry. 2008;18:2276–2280. doi: 10.1039/b800289d. DOI

Kostic R, et al. Vibrational spectroscopy of polypyrrole, theoretical-study. Journal of Chemical Physics. 1995;102:3104–3109. doi: 10.1063/1.468620. DOI

Liu Y-C, Hwang B-J. Identification of oxidized polypyrrole on Raman spectrum. Synthetic Metals. 2000;113:203–207. doi: 10.1016/S0379-6779(00)00188-0. DOI

Ishpal R, Kaur A. Spectroscopic and electrical sensing mechanism in oxidant-mediated polypyrrole nanofibers/nanoparticles for ammonia gas. Journal of Nanoparticle Research. 2013;15:1637. doi: 10.1007/s11051-013-1637-y. DOI

Wang H, et al. Microstructure, distribution and properties of conductive polypyrrole/cellulose fiber composites. Cellulose. 2013;20:1587–1601. doi: 10.1007/s10570-013-9945-z. DOI

El Jaouhari A, et al. Corrosion resistance and antibacterial activity of electrosynthesized polypyrrole. Synthetic Metals. 2017;226:15–24. doi: 10.1016/j.synthmet.2017.01.008. DOI

Jain S, 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;396:1317–1325. doi: 10.1016/j.apsusc.2016.11.154. DOI

Idla K., Talo A., Niemi H. E.-M., Forsén O., Yläsaari S. An XPS and AFM study of polypyrrole coating on mild steel. Surface and Interface Analysis. 1997;25(11):837–854. doi: 10.1002/(SICI)1096-9918(199710)25:11<837::AID-SIA307>3.0.CO;2-2. DOI

Schweiger B, Kim J, Kim YJ, Ulbricht M. Electropolymerized Molecularly Imprinted Polypyrrole Film for Sensing of Clofibric Acid. Sensors. 2015;15:4870–4889. doi: 10.3390/s150304870. PubMed DOI PMC

Ruangchuay L, Schwank J, Sirivat A. Surface degradation of α-naphthalene sulfonate-doped polypyrrole during XPS characterization. Applied Surface Science. 2002;199:128–137. doi: 10.1016/S0169-4332(02)00564-0. DOI

Wehrle B, Limbach H-H, Mortensen J, Heinze J. Solid-state 15N CPMAS NMR study of the structure of polypyrrole. Synthetic Metals. 1990;38:293–298. doi: 10.1016/0379-6779(90)90082-V. DOI

Ribó JM, Dicko A, Tura JM, Bloor D. Chemical structure of polypyrrole: X-ray photoelectron spectroscopy of polypyrrole with 5-yliden-3-pyrrolin-2-one end groups. Polymer. 1991;32:728–732. doi: 10.1016/0032-3861(91)90487-4. DOI

Kiani MS, Mitchell GR. The role of the counter-ion in the preparation of polypyrrole films with enhanced properties using a pulsed electrochemical potential. Synthetic Metals. 1992;48:203–218. doi: 10.1016/0379-6779(92)90062-N. DOI

Rajagopalan R, Iroh JO. Characterization of polyaniline–polypyrrole composite coatings on low carbon steel: a XPS and infrared spectroscopy study. Applied Surface Science. 2003;218:58–69. doi: 10.1016/S0169-4332(03)00579-8. DOI

Buitrago-Sierra R, Garcia-Fernandez MJ, Pastor-Blas MM, Sepulveda-Escribano A. Environmentally friendly reduction of a platinum catalyst precursor supported on polypyrrole. Green Chemistry. 2013;15:1981–1990. doi: 10.1039/c3gc40346g. DOI

Qin Y, Zhang T, Cui Z. Core-shell structure of polypyrrole grown on W18O49 nanorods for high performance gas sensor operating at room temperature. Organic Electronics. 2017;48:254–261. doi: 10.1016/j.orgel.2017.06.014. DOI

Rawal I, Sehrawat K, Kaur A. Vibrational spectroscopic investigations of ammonia gas sensing mechanism in polypyrrole nanostructures. Vibrational Spectroscopy. 2014;74:64–74. doi: 10.1016/j.vibspec.2014.07.012. DOI

Drbohlavova J, et al. Gold Nanostructured Surface for Electrochemical Sensing and Biosensing: Does Shape Matter? Analytical Letters. 2016;49:135–151. doi: 10.1080/00032719.2015.1043662. DOI

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