Plasma-Polymerized Thiophene-Reduced Graphene Oxide Composite Film Sensor for Ammonia/Amine Detection at Room Temperature

Industrialization has led to an increasing need for specific and selective gas sensors in the past few decades. Environmental monitoring of certain volatile compounds such as ammonia is necessary. Advancements in the food storage sector have created the need for cheap and effective amine chemosensors. Classical chemosensors still face several issues, such as a lack of selectivity and low sensitivity toward ammonia and amines. Sensitivity is defined as the relative change in response expressed in percentage. In this work, we have resolved a few issues associated with the ammonia and amine sensors, such as low selectivity, long-term instability, and unreliability under higher temperatures using plasma-polymerized thiophene (PPTh) reduced graphene oxide (rGO) composite films. PPTh films were prepared using RF plasma polymerization with optimized deposition parameters. Several samples were evaluated for their sensing response to understand the optimal PPTh and rGO ratio in the PPTh-rGO composite. These composite PPTh-rGO films have shown 4 times higher sensitivity for ammonia/amines than individual PPTh and rGO films. Ammonia, methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA) were primary analytes and tested for sensing response of the PPTh-rGO composite. The sensitivity measured ranges from 1328 for trimethylamine to 2354 for methylamine at 1000 ppm. The order of sensitivity was found to be MA > Ammonia > DMA > TMA. Polymer swelling, reduced charge carriers, and disruption of conductive pathways can explain possible sensing mechanisms. PPTh-rGO composite films have shown selectivity as high as 110 for ammonia/amine over other commonly used volatile organic compounds. The sensing response of these films is stable for any temperature fluctuations from 30 °C to 150 °C. Additionally, films showed stable sensitivity for over 4 months. Thus, composite films of PPTh-rGO can be effectively used to develop highly selective and stable gas sensors for the environmental monitoring of ammonia/amines.

[1]  Y. B. Khollam,et al.  Polyvinylpyrrolidone-Capped Silver Nanoparticles for Highly Sensitive and Selective Optical Fiber-Based Ammonium Sensor , 2022, Nanomaterials.

[2]  D. Correa,et al.  Recent Progress in Amine Gas Sensors for Food Quality Monitoring: Novel Architectures for Sensing Materials and Systems. , 2022, ACS sensors.

[3]  Yong Zhou,et al.  Mesoporous cellulose nanofibers-interlaced PEDOT:PSS hybrids for chemiresistive ammonia detection , 2022, Microchimica Acta.

[4]  B. Shin,et al.  Ultrafast Room Temperature Synthesis of Porous Polythiophene via Atmospheric Pressure Plasma Polymerization Technique and Its Application to NO2 Gas Sensors , 2021, Polymers.

[5]  Xiaojiao Wang,et al.  Adsorption, Gas-Sensing, and Optical Properties of Molecules on a Diazine Monolayer: A First-Principles Study , 2021, ACS omega.

[6]  R. Adelung,et al.  Improved Long‐Term Stability and Reduced Humidity Effect in Gas Sensing: SiO2 Ultra‐Thin Layered ZnO Columnar Films , 2021, Advanced Materials Technologies.

[7]  H. F. Hawari,et al.  Functionalized Reduced Graphene Oxide Thin Films for Ultrahigh CO2 Gas Sensing Performance at Room Temperature , 2021, Nanomaterials.

[8]  P. Jorge,et al.  Biosensors for Biogenic Amines: A Review , 2021, Biosensors.

[9]  Y. B. Khollam,et al.  Enhanced hydrogen gas sensing characteristics of graphene modified with rubidium (Rb) , 2021 .

[10]  A. Khan,et al.  Graphene synthesis, characterization and its applications: A review , 2021, Results in Chemistry.

[11]  S. Dhall,et al.  A review on environmental gas sensors: Materials and technologies , 2021, Sensors International.

[12]  S. Suprapto,et al.  Progress in Graphene Synthesis and its Application: History, Challenge and the Future Outlook for Research and Industry , 2020 .

[13]  Tadeusz Pustelny,et al.  Comparison of Gas Sensing Properties of Reduced Graphene Oxide Obtained by Two Different Methods , 2020, Sensors.

[14]  V. Mishra,et al.  Polymer/Graphene oxide nanocomposite thin film for NO2 sensor: An in situ investigation of electronic, morphological, structural, and spectroscopic properties , 2020, Scientific Reports.

[15]  A. Bajpai,et al.  CdSe nanorod-reinforced poly(thiophene) composites in designing energy storage devices: study of morphology and dielectric behavior , 2020, Polymer Bulletin.

[16]  Abdulazeez T. Lawal,et al.  Graphene-based nano composites and their applications. A review. , 2019, Biosensors & bioelectronics.

[17]  B. Liu,et al.  Synthesis, properties, and applications of graphene oxide/reduced graphene oxide and their nanocomposites , 2019, Nano Materials Science.

[18]  D. Mangalaraj,et al.  Porous reduced graphene oxide (rGO)/WO3 nanocomposites for the enhanced detection of NH3 at room temperature , 2019, Nanoscale advances.

[19]  F. Jia,et al.  Effect of Surfactants on the Microstructures of Hierarchical SnO2 Blooming Nanoflowers and their Gas-Sensing Properties , 2018, Nanoscale Research Letters.

[20]  Shivani A. Singh.  Investigation of PEG embedded WO3-graphene thin film sensor , 2017 .

[21]  R. Lavi,et al.  Multiple functionalization of tungsten disulfide inorganic nanotubes by covalently grafted conductive polythiophenes , 2016 .

[22]  Jincai Zhao,et al.  Fluorescent and photoconductive nanoribbons as a dual-mode sensor for selective discrimination of alkyl amines versus aromatic amines. , 2015, Chemical communications.

[23]  Teerakiat Kerdcharoen,et al.  Low-cost and flexible printed graphene–PEDOT:PSS gas sensor for ammonia detection , 2014 .

[24]  N. Huang,et al.  One-pot sonochemical synthesis of reduced graphene oxide uniformly decorated with ultrafine silver nanoparticles for non-enzymatic detection of H2O2 and optical detection of mercury ions , 2014 .

[25]  Robert H. Hurt,et al.  All in the graphene family - A recommended nomenclature for two-dimensional carbon materials , 2013 .

[26]  C. Lokhande,et al.  Temperature influence on morphological progress of Ni(OH)2 thin films and its subsequent effect on electrochemical supercapacitive properties , 2013 .

[27]  S. R. Thakare,et al.  Synthesis and characterization of silver nanoparticles embedded in polyaniline nanocomposite , 2013 .

[28]  D. Balogh,et al.  Optical chemical sensors using polythiophene derivatives as active layer for detection of volatile organic compounds , 2012 .

[29]  Y. B. Khollam,et al.  Polyethylene Oxide-Cu Composite Thick Films for Lpg Sensing , 2011 .

[30]  Lee E. Weiss,et al.  Inkjet printed chemical sensor array based on polythiophene conductive polymers , 2007 .

[31]  Hua Bai,et al.  Gas Sensors Based on Conducting Polymers , 2007, Sensors (Basel, Switzerland).

[32]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[33]  L. Martin,et al.  Growth vs. nucleation of conducting polymers thin films obtained by plasma-enhanced chemical vapor deposition , 2004 .

[34]  J. Feijen,et al.  On the iodine doping process of plasma polymerised thiophene layers , 2001 .

[35]  K. Kawata.  Development of mass-production-type plasma chemical vapour deposition equipment and its application to various dies , 1992 .