Inkjet-printed sol–gel films containing metal phthalocyanines/porphyrins for opto-electronic nose applications

Abstract In this work, five metal porphyrins and phthalocyanines embedded in transparent sol–gel films were deposited by piezoelectric inkjet printing, characterized and used as gas sensors. Explored compounds include magnesium/manganese(III) chloride/zinc 5,10,15,20-tetraphenyl-21H,23H-porphyrin, magnesium 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, and zinc 2,9,16,23-tetratertbutyl-29H,31H-phthalocyanine. Porphyrin/Phthalocyanine was blended with sol–gel solution to produce inks that were printed on glass substrates. The printed films were used as sensing layers for discrimination of volatile organic compounds (VOCs). Printed films were characterized by UV/vis spectroscopy, FTIR spectroscopy, and scanning electron microscopy. The employed sensing compounds are promising materials for optical gas sensors due to selective spectral alterations when exposed to oxidizing and reducing gases as well as VOCs. These alterations were observed by UV/vis spectroscopy and used to distinguish between several VOCs. To do so, a single printed sensing layer was exposed to methanol, ethanol, acetone and isopropanol vapor, respectively. During exposure the absorbance spectrum was continually measured and split into several wavelength intervals. By calculating the area integral of each interval and considering these as separate sensors it is possible to use a single sensing film to emulate sensor arrays. The results showed that the fabricated layers exhibit reversible optical modulations in the UV/vis spectra when exposed to various VOCs. The data have been analyzed by principal component analysis (PCA) and cluster analysis (CA). Results demonstrate the analytes to be distinguishable as isolated clusters in the PCA domains. The best results were obtained from ZnTPP and MgTPP containing films, whereas layers doped with Mn(III)ClTPP give unusable response.

[1]  Alberto Quaranta,et al.  Optical sensing properties of CoTPP thin films deposited by glow-discharge-induced sublimation , 2007 .

[2]  Meng-Sheng Liao,et al.  Electronic structure and bonding in metal phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg , 2001 .

[3]  Mira Josowicz,et al.  Composites of intrinsically conducting polymers as sensing nanomaterials. , 2008, Chemical reviews.

[4]  Ning Yan,et al.  Piezoelectric Ink‐Jet Printing of Horseradish Peroxidase: Effect of Ink Viscosity Modifiers on Activity , 2007 .

[5]  J Wang,et al.  Screen-printable sol-gel enzyme-containing carbon inks. , 1996, Analytical chemistry.

[6]  Pietro Siciliano,et al.  Spin-coated thin films of metal porphyrin-phthalocyanine blend for an optochemical sensor of alcohol vapours , 2004 .

[7]  Alberto Quaranta,et al.  Optical sensing responses of tetraphenyl porphyrins toward alcohol vapours: A comparison between vacuum evaporated and spin-coated thin films , 2007 .

[8]  G. D. Mea,et al.  Plasma-deposited copper phthalocyanine: A single gas-sensing material with multiple responses , 2008 .

[9]  S. K. Tripathi,et al.  Optical and infrared spectroscopic studies of chemical sensing by copper phthalocyanine thin films , 2008 .

[10]  Muhamad Mat Salleh,et al.  Self-assembled monolayer of copper(II) meso-tetra(4-sulfanatophenyl) porphyrin as an optical gas sensor , 2004 .

[11]  L. M. Davies,et al.  Development of a bioactive paper sensor for detection of neurotoxins using piezoelectric inkjet printing of sol-gel-derived bioinks. , 2009, Analytical chemistry.

[12]  C. Brinker,et al.  Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing , 1990 .

[13]  S. K. Tripathi,et al.  Effects of chemical analytes on zinc tetraphenylporphine thin films studied by vibrational spectroscopy and density functional theory , 2012 .

[14]  J. Simon,et al.  METALLOPHTHALOCYANINES. GAS SENSORS, RESISTORS AND FIELD EFFECT TRANSISTORS , 1998 .

[15]  S. K. Tripathi,et al.  Zinc phthalocyanine thin film and chemical analyte interaction studies by density functional theory and vibrational techniques , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[16]  P. Gemperline.  Practical Guide To Chemometrics , 2006 .

[17]  Dermot Diamond,et al.  Inkjet printed LED based pH chemical sensor for gas sensing. , 2009, Analytica chimica acta.

[18]  Pietro Siciliano,et al.  Metallophthalocyanines thin films in array configuration for electronic optical nose applications , 2003 .

[19]  H. Troy Nagle,et al.  Handbook of Machine Olfaction: Electronic Nose Technology , 2003 .

[20]  Pietro Siciliano,et al.  Optochemical vapour detection using spin coated thin film of ZnTPP , 2006 .

[21]  J. Garrido,et al.  Silica xerogels of tailored porosity as support matrix for optical chemical sensors. Simultaneous effect of pH, ethanol:TEOS and water:TEOS molar ratios, and synthesis temperature on gelation time, and textural and structural properties , 2007 .

[22]  Kenneth S Suslick,et al.  Colorimetric detection and identification of natural and artificial sweeteners. , 2009, Analytical chemistry.

[23]  C. Hunter,et al.  Detection of volatile organic compounds using porphyrin derivatives. , 2010, The journal of physical chemistry. B.

[24]  Sumio Sakka,et al.  Handbook of Sol-Gel Science and Technology : Processing Characterization and Applications , 2004 .

[25]  C. Malins,et al.  Nitrogen dioxide sensing characteristics at elevated temperature of sol–gel glass thin films containing substituted porphyrin dyes , 2001 .

[26]  Rui M. Almeida,et al.  Structural investigation of silica gel films by infrared spectroscopy , 1990 .

[27]  I. Jolliffe.  Principal Component Analysis , 2002 .

[28]  Teerakiat Kerdcharoen,et al.  Effect of Structural Transformation on the Gas-Sensing Properties of Phthalocyanine Thin Films , 2008 .

[29]  W. Stręk,et al.  Sensing abilities of materials prepared by sol–gel technology , 2009 .