Sorption and Diffusion of Water Vapor and Carbon Dioxide in Sulfonated Polyaniline as Chemical Sensing Materials

A hybrid quantum mechanics (QM)/molecular dynamics (MD) simulation is performed to investigate the effect of an ionizable group (–SO3−Na+) on polyaniline as gas sensing materials. Polymers considered for this work include emeraldine base of polyaniline (EB-PANI) and its derivatives (Na-SPANI (I), (II) and (III)) whose rings are partly monosubstituted by –SO3−Na+. The hybrid simulation results show that the adsorption energy, Mulliken charge and band gap of analytes (CO2 and H2O) in polyaniline are relatively sensitive to the position and the amounts of –SO3−Na+, and these parameters would affect the sensitivity of Na-SPANI/EB-PANI towards CO2. The sensitivity of Na-SPANI (III)/EB-PANI towards CO2 can be greatly improved by two orders of magnitude, which is in agreement with the experimental study. In addition, we also demonstrate that introducing –SO3−Na+ groups at the rings can notably affect the gas transport properties of polyaniline. Comparative studies indicate that the effect of ionizable group on polyaniline as gas sensing materials for the polar gas molecule (H2O) is more significant than that for the nonpolar gas molecule (CO2). These findings contribute in the functionalization-induced variations of the material properties of polyaniline for CO2 sensing and the design of new polyaniline with desired sensing properties.

[1]  M Meunier,et al.  Diffusion coefficients of small gas molecules in amorphous cis-1,4-polybutadiene estimated by molecular dynamics simulations. , 2005, The Journal of chemical physics.

[2]  Yadong Jiang,et al.  Fabrication and characterization of polyaniline-based gas sensor by ultra-thin film technology , 2002 .

[3]  W. Wlodarski,et al.  Polyaniline Nanofiber Based Surface Acoustic Wave Gas Sensors—Effect of Nanofiber Diameter on $\hbox{H}_{2}$ Response , 2007, IEEE Sensors Journal.

[4]  Steve Semancik,et al.  Controlled electrophoretic patterning of polyaniline from a colloidal suspension. , 2005, Journal of the American Chemical Society.

[5]  B. H. Weiller,et al.  Polyaniline nanofibers: facile synthesis and chemical sensors. , 2003, Journal of the American Chemical Society.

[6]  Cadmus Yuan,et al.  Validation of forcefields in predicting the physical and thermophysical properties of emeraldine base polyaniline , 2011 .

[7]  Tapash Chakraborty,et al.  Tunable band gap and magnetic ordering by adsorption of molecules on graphene , 2009, 0901.4956.

[8]  Yi He,et al.  Adsorption of Carbon Dioxide by MIL-101(Cr): Regeneration Conditions and Influence of Flue Gas Contaminants , 2013, Scientific Reports.

[9]  Ting Zhang,et al.  Electrochemically Functionalized Single‐Walled Carbon Nanotube Gas Sensor , 2006 .

[10]  Milind V. Kulkarni,et al.  Polyaniline and its substituted derivatives as sensor for aliphatic alcohols , 2000 .

[11]  Junfa Zhu,et al.  Post-combustion CO2 capture with the HKUST-1 and MIL-101(Cr) metal–organic frameworks: Adsorption, separation and regeneration investigations , 2013 .

[12]  A. J. Epstein,et al.  Synthesis and Physical Properties of Highly Sulfonated Polyaniline , 1996 .

[13]  A. Heeger,et al.  Flexible light-emitting diodes made from soluble conducting polymers , 1992, Nature.

[14]  Xinli Jing,et al.  Intrinsically conducting polymers for electromagnetic interference shielding , 2005 .

[15]  Guo-Qi Zhang,et al.  Ab Initio Study of Temperature, Humidity, and Covalent Functionalization-Induced Bandgap Change of Single-Walled Carbon Nanotubes , 2015, IEEE Electron Device Letters.

[16]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[17]  Jing Liang,et al.  Functional Materials for Rechargeable Batteries , 2011, Advanced materials.

[18]  Noel D.G. White,et al.  Development of carbon dioxide (CO2) sensor for grain quality monitoring , 2010 .

[19]  Richard B. Kaner,et al.  Polyaniline Nanofiber Gas Sensors: Examination of Response Mechanisms , 2004 .

[20]  Cadmus Yuan,et al.  Impact of the functional group on the working range of polyaniline as carbon dioxide sensors , 2012 .

[21]  Anjali A. Athawale,et al.  Chloroform vapour sensor based on copper/polyaniline nanocomposite , 2002 .

[22]  Alan J. Heeger,et al.  Self-doped conducting polymers , 1987 .

[23]  A. MacDiarmid,et al.  "Synthetic Metals": A Novel Role for Organic Polymers (Nobel Lecture). , 2001, Angewandte Chemie.

[24]  Cees J.M. van Rijn,et al.  Carbon dioxide sensing with sulfonated polyaniline , 2012 .

[25]  Muhammad Sahimi,et al.  Molecular dynamics simulation of diffusion and sorption of water in conducting polyaniline. , 2007, The Journal of chemical physics.

[26]  Muhammad Sahimi,et al.  Water Sorption of Acid-Doped Polyaniline Solid Fibers: Equilibrium and Kinetic Response , 2005 .

[27]  Chuin-Shan Chen,et al.  First-Principles Surface Stress Calculations and Multiscale Deformation Analysis of a Self-Assembled Monolayer Adsorbed on a Micro-Cantilever , 2014, Sensors.

[28]  Anjali A. Athawale,et al.  Nanocomposite of Pd-polyaniline as a selective methanol sensor , 2006 .

[29]  K. Varahramyan,et al.  Humidity sensor based on ultrathin polyaniline film deposited using layer-by-layer nano-assembly , 2006 .

[30]  W. Wlodarski,et al.  Hydrogen gas sensor based on highly ordered polyaniline nanofibers , 2009 .

[31]  Michael O'Keeffe,et al.  Control of pore size and functionality in isoreticular zeolitic imidazolate frameworks and their carbon dioxide selective capture properties. , 2009, Journal of the American Chemical Society.

[32]  Felix A. Miranda,et al.  Electrospun polyaniline/polyethylene oxide nanofiber field-effect transistor , 2003 .

[33]  Cadmus Yuan,et al.  Molecular modeling of temperature dependence of solubility parameters for amorphous polymers , 2011, Journal of Molecular Modeling.

[34]  Cadmus Yuan,et al.  Molecular model for the charge carrier density dependence of conductivity of polyaniline as chemical sensing materials , 2013 .

[35]  Stanley Y. Y. Leung,et al.  Functionalization-induced changes in the structural and physical properties of amorphous polyaniline: a first-principles and molecular dynamics study , 2016, Scientific Reports.

[36]  Rajender S Varma,et al.  Aqueous microwave chemistry: a clean and green synthetic tool for rapid drug discovery. , 2008, Chemical Society reviews.

[37]  P. K. Shen,et al.  A Study of Tungsten Trioxide and Polyaniline Composite Films I . Electrochemical and Electrochromic Behavior , 1992 .

[38]  Y. Duan,et al.  An improved optical pH sensor based on polyaniline , 2000 .

[39]  Menghe Miao,et al.  High‐Performance Two‐Ply Yarn Supercapacitors Based on Carbon Nanotubes and Polyaniline Nanowire Arrays , 2013, Advanced materials.

[40]  Arthur J. Epstein,et al.  Effect of sulfonic acid group on polyaniline backbone , 1991 .

[41]  Peng Li,et al.  Corrosion protection of mild steel by electroactive polyaniline coatings , 1997 .

[42]  Khurshid Ayub,et al.  DFT Study of Polyaniline NH3, CO2, and CO Gas Sensors: Comparison with Recent Experimental Data , 2013 .

[43]  X. P. Chen,et al.  First-principles study of the effect of functional groups on polyaniline backbone , 2015, Scientific Reports.

[44]  W. Wlodarski,et al.  Layered SAW gas sensor based on CSA synthesized polyaniline nanofiber on AlN on 64° YX LiNbO3 for H2 sensing , 2009 .

[45]  Muhammad Sahimi,et al.  Water sorption of acid-doped polyaniline powders and hollow fibers : Equilibrium and kinetic response , 2006 .

[46]  Muhammad Sahimi,et al.  Water harvesting using a conducting polymer: a study by molecular dynamics simulation. , 2009, Physical review. E, Statistical, nonlinear, and soft matter physics.