Sub-ppm Formaldehyde Detection by n-n TiO2@SnO2 Nanocomposites

Formaldehyde (HCHO) is an important indicator of indoor air quality and one of the markers for detecting lung cancer. Both medical and air quality applications require the detection of formaldehyde in the sub-ppm range. Nanocomposites SnO2/TiO2 are promising candidates for HCHO detection, both in dark conditions and under UV illumination. Nanocomposites TiO2@SnO2 were synthesized by ALD method using nanocrystalline SnO2 powder as a substrate for TiO2 layer growth. The microstructure and composition of the samples were characterized by ICP-MS, TEM, XRD and Raman spectroscopy methods. The active surface sites were investigated using FTIR and TPR-H2 methods. The mechanism of formaldehyde oxidation on the surface of semiconductor oxides was studied by in situ DRIFTS method. The sensor properties of nanocrystalline SnO2 and TiO2@SnO2 nanocomposites toward formaldehyde (0.06–0.6 ppm) were studied by in situ electrical conductivity measurements in dark conditions and under periodic UV illumination at 50–300 °C. Nanocomposites TiO2@SnO2 exhibit a higher sensor signal than SnO2 and a decrease in the optimal measurement temperature by 50 °C. This result is explained based on the model considering the formation of n-n heterocontact at the SnO2/TiO2 interface. UV illumination leads to a decrease in sensor response compared with that obtained in dark conditions because of the photodesorption of oxygen involved in the oxidation of formaldehyde.

[1]  Akira Fujishima,et al.  Photocatalytic Degradation of Gaseous Formaldehyde Using TiO2 Film , 1998 .

[2]  Yong Xu,et al.  The absolute energy positions of conduction and valence bands of selected semiconducting minerals , 2000 .

[3]  K. Butler,et al.  Polymorph Engineering of TiO2: Demonstrating How Absolute Reference Potentials Are Determined by Local Coordination , 2015 .

[4]  Xin Sheng Li,et al.  Enhancement of hydrogen spillover by surface labile oxygen species on oxidized Pt/TiO2 catalyst , 1995 .

[5]  C. Xie,et al.  La2O3-sensitized SnO2 nanocrystalline porous film gas sensors and sensing mechanism toward formaldehyde , 2013 .

[6]  Mengmeng Li,et al.  Zeolitic Imidazolate Framework Coated ZnO Nanorods as Molecular Sieving to Improve Selectivity of Formaldehyde Gas Sensor , 2016 .

[7]  J. Morante,et al.  Raman Surface Vibration Modes in Nanocrystalline SnO2: Correlation with Gas Sensor Performances , 2005 .

[8]  Hengfu Shui,et al.  Investigation on formaldehyde gas sensor with ZnO thick film prepared through microwave heating method , 2009 .

[9]  P. Chu,et al.  Identification of oxygen vacancy types from Raman spectra of SnO2 nanocrystals , 2012 .

[10]  F. Rojas,et al.  Studies of sol–gel TiO2 and Pt/TiO2 catalysts for NO reduction by CO in an oxygen-rich condition , 2004 .

[11]  Derek R. Miller,et al.  Nanoscale metal oxide-based heterojunctions for gas sensing: A review , 2014 .

[12]  Changsheng Xie,et al.  Fabrication and formaldehyde gas-sensing property of ZnO–MnO2 coplanar gas sensor arrays , 2010 .

[13]  H. Haick,et al.  Sensors for breath testing: from nanomaterials to comprehensive disease detection. , 2014, Accounts of chemical research.

[14]  P. P. Lottici,et al.  Phonon confinement effects in the Raman scattering by TiO2 nanocrystals , 1998 .

[15]  Liang Peng,et al.  Size- and photoelectric characteristics-dependent formaldehyde sensitivity of ZnO irradiated with UV light , 2010 .

[16]  Angel Diéguez,et al.  The complete Raman spectrum of nanometric SnO 2 particles , 2001 .

[17]  Xiaogan Li,et al.  Room temperature impedance spectroscopy-based sensing of formaldehyde with porous TiO2 under UV illumination , 2013 .

[18]  K. S. Krishnan,et al.  The Raman Effect in Crystals , 1928, Nature.

[19]  Changsheng Xie,et al.  A comparative study on UV light activated porous TiO2 and ZnO film sensors for gas sensing at room temperature , 2012 .

[20]  Sheikh A. Akbar,et al.  A selective room temperature formaldehyde gas sensor using TiO2 nanotube arrays , 2011 .

[21]  Changsheng Xie,et al.  UV light activation of TiO2 for sensing formaldehyde: How to be sensitive, recovering fast, and humidity less sensitive , 2014 .

[22]  G. Busca,et al.  FT-IR study of the adsorption and transformation of formaldehyde on oxide surfaces , 1987 .

[23]  Yangong Zheng,et al.  Formaldehyde gas sensor based on SnO2/In2O3 hetero-nanofibers by a modified double jets electrospinning process , 2012 .

[24]  G. Tompsett,et al.  The Raman spectrum of brookite, TiO2 (Pbca, Z = 8) , 1995 .

[25]  Jing Wang,et al.  An enrichment method to detect low concentration formaldehyde , 2008 .

[26]  Yumin Zhang,et al.  A high sensitivity gas sensor for formaldehyde based on silver doped lanthanum ferrite , 2014 .

[27]  J. Bae,et al.  Bandgap-designed TiO2/SnO2 hollow hierarchical nanofibers: synthesis, properties, and their photocatalytic mechanism , 2016 .

[28]  B. Mondal,et al.  Facile synthesis of pseudo-peanut shaped hematite iron oxide nano-particles and their promising ethanol and formaldehyde sensing characteristics , 2014 .

[29]  Hong-Qing He,et al.  Theoretical and experimental analysis on vibrational spectra of formate species adsorbed on Cu–Al2O3 catalyst , 2008 .

[30]  M. Rumyantseva,et al.  Photosensitive Organic-Inorganic Hybrid Materials for Room Temperature Gas Sensor Applications , 2018, Nanomaterials.

[31]  K. Prabakar,et al.  Titanium oxide prepared by polymer gel assisted combustion method for dye-sensitized solar cell , 2011 .

[32]  Kiran Chikkadi,et al.  E-Nose Sensing of Low-ppb Formaldehyde in Gas Mixtures at High Relative Humidity for Breath Screening of Lung Cancer? , 2016 .

[33]  N. Yamazoe,et al.  Hollow SnO2/α-Fe2O3 spheres with a double-shell structure for gas sensors , 2014 .

[34]  K. Zhao,et al.  Synthesis of TiO2 nanofibers with adjustable anatase/rutile ratio from Ti sol and rutile nanoparticles for the degradation of pollutants in wastewater , 2015 .

[35]  R. O’Hayre,et al.  The Role of Nanoscale Seed Layers on the Enhanced Performance of Niobium doped TiO2 Thin Films on Glass , 2016, Scientific Reports.

[36]  Sotiris E. Pratsinis,et al.  Selective sensing of isoprene by Ti-doped ZnO for breath diagnostics. , 2016, Journal of materials chemistry. B.

[37]  Ning Han,et al.  CdO activated Sn-doped ZnO for highly sensitive, selective and stable formaldehyde sensor , 2011 .

[38]  T. Zhu,et al.  Heterogeneous reaction of formaldehyde on the surface of γ-Al2O3 particles , 2011 .

[39]  Ping Wang,et al.  Ultraviolet-assisted gas sensing: A potential formaldehyde detection approach at room temperature based on zinc oxide nanorods , 2009 .

[40]  P. Zapata,et al.  FTIR and Raman Characterization of TiO2 Nanoparticles Coated with Polyethylene Glycol as Carrier for 2-Methoxyestradiol , 2017 .

[41]  Mohd Faizul Mohd Sabri,et al.  Enhanced Ethanol Gas Sensing Properties of SnO2-Core/ZnO-Shell Nanostructures , 2014, Sensors.

[42]  C. S. Ferreira,et al.  Rice Husk Reuse in the Preparation of SnO2/SiO2Nanocomposite , 2015 .

[43]  Shawn D. Lin,et al.  In situ DRIFTS study on the methanol oxidation by lattice oxygen over Cu/ZnO catalyst , 2011 .

[44]  T. V. Andrushkevich,et al.  Identification of adsorption forms by ir spectroscopy for formaldehyde and formic acid on K3PMo12O40 , 1997 .

[45]  Supab Choopun,et al.  Low temperature ethanol response enhancement of ZnO nanostructures sensor decorated with gold nanoparticles exposed to UV illumination , 2016 .

[46]  Ghenadii Korotcenkov,et al.  Metal oxide composites in conductometric gas sensors: Achievements and challenges , 2017 .

[47]  M. Crocker,et al.  Catalytic removal of formaldehyde at room temperature over supported gold catalysts , 2013 .

[48]  Fariborz Taghipour,et al.  UV-LED Photo-activated Chemical Gas Sensors: A Review , 2017 .

[49]  Giovanni Neri,et al.  Detection of hazardous volatile organic compounds (VOCs) by metal oxide nanostructures-based gas sensors: A review , 2016 .

[50]  I. Castro-Hurtado,et al.  Conductometric formaldehyde gas sensors. A review: From conventional films to nanostructured materials , 2013 .

[51]  Kun Liu,et al.  The role of brookite in mechanical activation of anatase-to-rutile transformation of nanocrystalline TiO2: An XRD and Raman spectroscopy investigation , 2011 .

[52]  G. Socrates,et al.  Infrared and Raman characteristic group frequencies : tables and charts , 2001 .

[53]  Wei Li,et al.  Au@ZnO core–shell structure for gaseous formaldehyde sensing at room temperature , 2014 .

[54]  Guangfen Wei,et al.  Recognizing indoor formaldehyde in binary gas mixtures with a micro gas sensor array and a neural network , 2007 .

[55]  K. Nakamoto Infrared and Raman Spectra of Inorganic and Coordination Compounds , 1978 .

[56]  L. Abello,et al.  Structural Characterization of Nanocrystalline SnO2by X-Ray and Raman Spectroscopy , 1998 .

[57]  Y. Qian,et al.  Study of the Raman spectrum of nanometer SnO2 , 1994 .

[58]  Wei Zhang,et al.  Photoluminescence in anatase titanium dioxide nanocrystals , 2000 .

[59]  Zhongchang Wang,et al.  Sensitivity improvement of TiO2-doped SnO2 to volatile organic compounds , 2010 .

[60]  C. Xie,et al.  In situ diffuse reflectance infrared Fourier transform spectroscopy study of formaldehyde adsorption and reactions on nano γ-Fe2O3 films , 2013 .

[61]  Mark Miodownik,et al.  Highly parallel computer simulations of particle pinning: zener vindicated , 2000 .

[62]  R. Dhaka,et al.  Design of a graphene oxide-SnO2 nanocomposite with superior catalytic efficiency for the synthesis of β-enaminones and β-enaminoesters , 2015 .

[63]  M. Rumyantseva,et al.  Chemical modification of nanocrystalline metal oxides: effect of the real structure and surface chemistry on the sensor properties , 2008 .

[64]  W. Maziarz,et al.  Structural, optical and electrical properties of nanocrystalline TiO2, SnO2 and their composites obtained by the sol–gel method , 2016 .

[65]  M. Li,et al.  Preparation of anatase/rutile TiO2/SnO2 hollow heterostructures for gas sensor , 2018, Journal of Alloys and Compounds.

[66]  J. Piqueras,et al.  Growth and characterization of Cr doped SnO2 microtubes with resonant cavity modes , 2016 .

[67]  Chen Gao,et al.  Photocatalytic Oxidation of Gaseous Formaldehyde on TiO2: An In Situ DRIFTS Study , 2010 .

[68]  A. Srivastava,et al.  Shape control synthesis, characterizations, mechanisms and optical properties of large scaled metal oxide nanostructures of ZnO and TiO 2 , 2015 .

[69]  Jian-ming Hong,et al.  Size effect on phase transition sequence of TiO2 nanocrystal , 2005 .

[70]  H. Kleebe,et al.  Gas sensing properties of TiO2 - SnO2 nanomaterials , 2013 .

[71]  Jun Yu,et al.  Study on a micro-gas sensor with SnO2–NiO sensitive film for indoor formaldehyde detection , 2008 .

[72]  Wen Zeng,et al.  Selective Detection of Formaldehyde Gas Using a Cd-Doped TiO2-SnO2 Sensor , 2009, Sensors.

[73]  J. Banfield,et al.  UNDERSTANDING POLYMORPHIC PHASE TRANSFORMATION BEHAVIOR DURING GROWTH OF NANOCRYSTALLINE AGGREGATES: INSIGHTS FROM TIO2 , 2000 .

[74]  Liang Peng,et al.  Light induced enhancing gas sensitivity of copper-doped zinc oxide at room temperature , 2008 .

[75]  Dan Chen,et al.  Identification of reaction intermediates and mechanism responsible for highly active HCHO oxidation on Ag/MCM-41 catalysts , 2013 .

[76]  M. Rumyantseva,et al.  Doping effects on electrical and optical properties of spin-coated ZnO thin films , 2015 .

[77]  Vinayak P. Dravid,et al.  UV-activated room-temperature gas sensing mechanism of polycrystalline ZnO , 2009 .

[78]  J. Gomes,et al.  A theoretical study of dioxymethylene, proposed as intermediate in the oxidation of formaldehyde to formate over copper , 2000 .

[79]  Xiaogan Li,et al.  Preparation of Cd-Loaded In2O3 Hollow Nanofibers by Electrospinning and Improvement of Formaldehyde Sensing Performance , 2014 .

[80]  Xinxin Xing,et al.  Formaldehyde detection: SnO2 microspheres for formaldehyde gas sensor with high sensitivity, fast response/recovery and good selectivity , 2017 .

[81]  M. Rumyantseva,et al.  Nanocomposites SnO2/SiO2 for CO Gas Sensors: Microstructure and Reactivity in the Interaction with the Gas Phase , 2019, Materials.

[82]  Nak-Jin Choi,et al.  A ppb-level formaldehyde gas sensor based on CuO nanocubes prepared using a polyol process , 2014 .

[83]  Marina Rumyantseva,et al.  Visible light activation of room temperature NO2 gas sensors based on ZnO, SnO2 and In2O3 sensitized with CdSe quantum dots , 2016 .

[84]  S. Bai,et al.  Ag decorated SnO2 nanoparticles to enhance formaldehyde sensing properties , 2019, Journal of Physics and Chemistry of Solids.

[85]  Frank J. Kelly,et al.  WHO Guidelines for Indoor Air Quality: Selected pollutants. , 2010 .

[86]  I. Castro-Hurtado,et al.  SnO2-nanowires grown by catalytic oxidation of tin sputtered thin films for formaldehyde detection , 2012 .

[87]  Xiaogan Li,et al.  Highly sensitive and selective room-temperature formaldehyde sensors using hollow TiO2 microspheres , 2015 .

[88]  S. Sahoo,et al.  Titanium dioxide synthesized using titanium chloride: size effect study using Raman spectroscopy and photoluminescence , 2009 .

[89]  M. Rumyantseva,et al.  Detection of Carbon Monoxide in Humid Air with Double-Layer Structures Based on Semiconducting Metal Oxides and Silicalite , 2018, Russian Journal of Applied Chemistry.

[90]  Dan Han,et al.  Synthesis and formaldehyde sensing performance of LaFeO3 hollow nanospheres , 2014 .

[91]  Feng-Chao Chung,et al.  Fabrication of a Au@SnO2 core–shell structure for gaseous formaldehyde sensing at room temperature , 2014 .

[92]  C. Xiong,et al.  Investigation of Raman spectrum for nano-SnO2 , 1997 .

[93]  Peder Wolkoff,et al.  Re-evaluation of the WHO (2010) formaldehyde indoor air quality guideline for cancer risk assessment , 2016, Archives of Toxicology.

[94]  M. Rumyantseva,et al.  Selective detection of individual gases and CO/H 2 mixture at low concentrations in air by single semiconductor metal oxide sensors working in dynamic temperature mode , 2018 .

[95]  Arno Schmidt-Trucksäss,et al.  Breath Sensors for Health Monitoring. , 2019, ACS sensors.

[96]  Pengyi Zhang,et al.  Review on noble metal-based catalysts for formaldehyde oxidation at room temperature , 2019, Applied Surface Science.

[97]  I. Castro-Hurtado,et al.  Studies of influence of structural properties and thickness of NiO thin films on formaldehyde detection , 2011 .

[98]  B. Zhang,et al.  Synthesis of novel porous ZnO octahedrons and their improved UV-light activated formaldehyde-sensing performance by Au decoration , 2019, Physica E: Low-dimensional Systems and Nanostructures.

[99]  Qin Zhu,et al.  A highly sensitive and selective formaldehyde gas sensor using a molecular imprinting technique based on Ag–LaFeO3 , 2014 .

[100]  H. Ho,et al.  Light-Activated Metal Oxide Gas Sensors: A Review , 2017, Micromachines.

[101]  Hong He,et al.  Catalytic performance and mechanism of a Pt/TiO2 catalyst for the oxidation of formaldehyde at room temperature , 2006 .

[102]  Sotiris E. Pratsinis,et al.  Zeolite membranes for highly selective formaldehyde sensors , 2018 .

[103]  Richard J. Ewen,et al.  Highly sensitive room temperature sensors based on the UV-LED activation of zinc oxide nanoparticles , 2008 .

[104]  B. Morosin,et al.  Pressure and Temperature Dependences of the Raman-Active Phonons in Sn O 2 , 1973 .

[105]  Marina N. Rumyantseva,et al.  Nanocrystalline SnO2 and In2O3 as materials for gas sensors: The relationship between microstructure and oxygen chemisorption , 2009 .

[106]  Jing Zhu,et al.  Hierarchically porous indium oxide nanolamellas with ten-parts-per-billion-level formaldehyde-sensing performance , 2015 .

[107]  Yanhong Lin,et al.  Study on photoelectric gas-sensing property and photogenerated carrier behavior of Ag–ZnO at the room temperature , 2013 .

[108]  K. Zakrzewska,et al.  Sensitization of TiO2/SnO2 nanocomposites for gas detection , 2013 .

[109]  Hossam Haick,et al.  Volatile organic compounds of lung cancer and possible biochemical pathways. , 2012, Chemical reviews.

[110]  Rong-Hua Ma,et al.  A self-heating gas sensor with integrated NiO thin-film for formaldehyde detection , 2007 .

[111]  Jing Wang,et al.  Preparation and characterization of La1−xSrxFeO3 materials and their formaldehyde gas-sensing properties , 2012, Journal of Materials Science.

[112]  N. Bârsan,et al.  Quenched, nanocrystalline In4Sn3O12 high temperature phase for gas sensing applications , 2012 .

[113]  K. Nakamoto Theory and applications in inorganic chemistry , 2009 .

[114]  Jing Wang,et al.  Silicon-based micro-gas sensors for detecting formaldehyde , 2009 .

[115]  Chen Yingxu,et al.  Catalytic activities of CuO/TiO2 and CuO-ZrO2/TiO2 in NO + CO reaction , 2004 .

[116]  W. Miekisch,et al.  Breath gas aldehydes as biomarkers of lung cancer , 2009, International journal of cancer.

[117]  Janusz Smulko,et al.  Fluctuation enhanced gas sensing with WO3-based nanoparticle gas sensors modulated by UV light at selected wavelengths , 2016 .

[118]  Ning Han,et al.  Improving humidity selectivity in formaldehyde gas sensing by a two-sensor array made of Ga-doped ZnO , 2009 .

[119]  V. Dobrokhotov,et al.  Multisensory Gas Chromatography for Field Analysis of Complex Gaseous Mixtures , 2019, ChemEngineering.

[120]  Hui Yang,et al.  Zeolitic imidazolate framework as formaldehyde gas sensor. , 2014, Inorganic chemistry.

[121]  Zhen-Lai Zhou,et al.  The fabrication and gas-sensing characteristics of the formaldehyde gas sensors with high sensitivity , 2008 .

[122]  Ke Dai,et al.  Highly selective n-butanol gas sensor based on mesoporous SnO2 prepared with hydrothermal treatment , 2014 .