Plasma-enabled sensing of urea and related amides on polyaniline

Abstract

The atmospheric pressure plasma jet (APPJ) was used to enhance the sensitivity of industrially important polyaniline (PANI) for detection of organic vapors from amides. The gas sensing mechanism of PANI is operating on the basis of reversible protonation or deprotonation, whereas the driving force to improve the sensitivity after plasma modifications is unknown. Herein we manage to solve this problem and investigate the sensing mechanism of atmospheric plasma treated PANI for vapor detection of amides using urea as a model. The results from various analytical techniques indicate that the plausible mechanism responsible for the improved sensitivity after plasma treatment is operating through a cyclic transition state formed between the functional groups introduced by plasma treatment and urea. This transition state improved the sensitivity of PANI towards 15 ppm of urea by a factor of 2.4 times compared to the non-treated PANI. This plasma treated PANI is promising for the improvement of the sensitivity and selectivity towards other toxic and carcinogenic amide analytes for gas sensing applications such as improving material processing and controlling food quality.

Graphical abstract

Keywords

gas sensing / urea / PANI / amides / plasma

References

[1] Macdiarmid A G, Chiang J C, Richter A F, Epstein A J. Polyaniline: A new concept in conducting polymers. Synthetic Metals, 1987, 18: 285–290

[2] Hao B, Li L, Wang Y, Qian H, Tong G, Chen H, Chen K. Electrical and microwave absorbing properties of polypyrrole synthesized by optimum strategy. Journal of Applied Polymer Science, 2013, 127: 4273–4279

[3] Trivedi D C. Polyanilines. In: Nalwa H S, ed. Handbook of Organic Conductive Molecules and Polymers, vol. 2. New Jersey: John Wiley & Sons, 1997, 505

[4] Ayad M M, El-Hefnawey G, Torad N L. A sensor of alcohol vapours based on thin polyaniline base film and quartz crystal microbalance. Journal of Hazardous Materials, 2009, 168: 85–88

[5] Nicolas-Debarnot D, Poncin-Epaillard F. Polyaniline as a new sensitive layer for gas sensors. Analytica Chimica Acta, 2003, 475: 1–15

[6] Zhang X, Qin Z, Liu X, Liang B, Liu N, Zhou Z, Zhu M. Flexible sensing fibers based on polyaniline-coated polyurethane for chloroform vapor detection. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1: 10327–10333

[7] Jaymand M. Recent progress in chemical modification of polyaniline. Progress in Polymer Science, 2013, 38: 1287–1306

[8] Kang E T, Ma Z H, Tan K L, Zhu B R, Uyama Y, Ikada Y. Surface modification and functionalization of electroactive polymer films. Polymers for Advanced Technologies, 1999, 10: 421–428

[9] Kang E T, Kato K, Uyama Y, Ikada Y. Plasma treatment of polyaniline films: Effect on the intrinsic oxidation states. Journal of Materials Research, 1996, 11: 1570–1573

[10] Kunzo P, Lobotka P, Micusik M, Kovacova E. Palladium-free hydrogen sensor based on oxygen-plasma-treated polyaniline thin film. Sensors and Actuators. B, Chemical, 2012, 171-172: 838–845

[11] Yoo K P, Kwon K H, Min N K, Lee M J, Lee C J. Effects of O₂ plasma treatment on NH₃ sensing characteristics of multiwall carbon nanotube/polyaniline composite films. Sensors and Actuators. B, Chemical, 2009, 143: 333–340

[12] Du H Y, Wang J, Yao P J, Hao Y W, Li X G. Preparation of modified MWCNTs-doped PANI nanorods by oxygen plasma and their ammonia-sensing properties. Journal of Materials Science, 2013, 48: 3597–3604

[13] Koebel M, Elsener M. Determination of urea and its thermal decomposition products by high-performance liquid chromatography. Journal of Chromatography. A, 1995, 689: 164–169

[14] Bertocci P, Compagnone D, Palleschi G. Amperometric ammonium ion and urea determination with enzyme-based probes. Biosensors and Bioelectronics, 1996, 11: 1–10

[15] Palmqvist E, Kriz C B, Svanberg K, Khayyami M, Kriz D. DC-resistometric urea sensitive device utilizing a conducting polymer film for the gas-phase detection of ammonia. Biosensors & Bioelectronics, 1995, 10: 283–287

[16] Stejskal J, Gilbert R G. Polyaniline: Preparation of a conducting polymer (IUPAC technical report). Pure and Applied Chemistry, 2002, 74: 857–867

[17] Zaplotnik R, Bišćan M, Kregar Z, Vesel A, Cvelbar U, Mozetic M, Milošević S. Influence of a samples surface on single electrode atmospheric pressure plasma jet parameters. Spectrochemica acta B, 2014, 103/104: 124–130

[18] Zaplotnik R, Kregar Z, Bišćan M, Vesel A, Cvelbar U, Mozetic M, Milošević S. Multiple vs. single harmonics AC-driven atmospheric pressure plasma jet. Europhysics Letters, 2014, 106: 25001

[19] Niu L, Luo Y, Li Z. A highly selective chemical gas sensor based on functionalization of multi-walled carbon nanotubes with poly(ethylene glycol). Sensors and Actuators. B, Chemical, 2007, 126: 361–367

[20] Slobodian P, Riha P, Lengalova A, Svoboda P, Saha P. Multi-wall carbon nanotube networks as potential resistive gas sensors for organic vapor detection. Carbon, 2011, 49: 2499–2507

[21] Wen N, Brooker M H. Urea protonation: Raman and theoretical study. Journal of Physical Chemistry, 1993, 97: 8608–8616

[22] Kang E T, Ma Z H, Tan K L, Zhu B R, Uyama Y, Ikada Y. Surface modification and functionalization of electroactive polymer films. Polymers for Advanced Technologies, 1999, 10: 421–428

[23] Puliyalil H, Cvelbar U, Filipič G, Petrič A D, Zaplotnik R, Recek N, Mozetič M, Thomas S. Plasma as a tool for enhancing insulation properties of polymer composites. RSC Advances, 2015, 5: 37853–37858

[24] Qaiser A A, Hyland M M, Patterson D A. Surface and charge transport characterization of polyaniline-cellulose acetate composite membranes. Journal of Physical Chemistry B, 2011, 115: 1652–1661

[25] Peng H, Mo Z, Liao S, Liang H, Yang L, Luo F, Song H, Zhong Y, Zhang B. High performance Fe- and N- doped carbon catalyst with graphene structure for oxygen reduction. Scientific Reports, 2013, 3: 1765

[26] Batich C D, Donald D S. X-ray photoelectron spectroscopy of nitroso compounds: Relative ionicity of the closed and open forms. Journal of the American Chemical Society, 1984, 106: 2758–2761

[27] Angelopoulos M, Asturias G E, Ermer S P, Ray A, Scherr E M, Macdiarmid A G, Akhtar M, Kiss Z, Epstein A J. Polyaniline: Solutions, films and oxidation state. Molecular Crystals and Liquid Crystals Incorporating Nonlinear Optics, 1988, 160: 151–163

[28] Trchová M, Stejskal J. Polyaniline: The infrared spectroscopy of conducting polymer nanotubes. Pure and Applied Chemistry, 2011, 83: 1803–1817

[29] Boer F P, Shannon T W, Mclafferty F W. Electronic structure of the six-membered cyclic transition state in some gamma hydrogen rearrangements. Journal of the American Chemical Society, 1968, 90: 7239–7248

[30] Ostrikov K, Yoon N J, Rider A E, Vladimirov S V. Two-dimensional simulation of nanoassembly precursor species in Ar+H₂+C₂H₂ reactive plasmas. Plasma Processes and Polymers, 2007, 4: 27–40

[31] Arockiam P B, Bruneau C, Dixneuf P H. Ruthenium (II)-catalyzed C–H bond activation and functionalization. Chemical Reviews, 2012, 112: 5879–5918

[32] Dang Y, Qu S, Nelson J W, Pham H D, Wang Z X, Wang X. The mechanism of a ligand-promoted sp³ C–H activation and arylation reaction via palladium catalysis: Theoretical demonstration of a Pd(II)/Pd(IV) redox manifold. Journal of the American Chemical Society, 2015, 137: 2006–2014

Acknowledgements

This project was supported by the Slovenian Research Agency (ARRS) project L2-6769, and by the Ministry of Education, Youth and Sports of the Czech Republic—program NPU I (LO1504). H.P thanks Jozef Stefan International Postgraduate School (MPŠ) for the PhD grant. KO thanks the Australian Research Council and CSIRO Science Leadership Program for partial support.

RIGHTS & PERMISSIONS

2016 Higher Education Press and Springer-Verlag Berlin Heidelberg