Single and Networked ZnO-CNT Hybrid Tetrapods for Selective Room-Temperature High-Performance Ammonia Sensors.

Highly porous hybrid materials with unique high-performance properties have attracted great interest from the scientific community, especially in the field of gas-sensing applications. In this work, tetrapodal-ZnO (ZnO-T) networks were functionalized with carbon nanotubes (CNTs) to form a highly efficient hybrid sensing material (ZnO-T-CNT) for ultrasensitive, selective, and rapid detection of ammonia (NH3) vapor at room temperature. By functionalizing the ZnO-T networks with 2.0 wt % of CNTs by a simple dripping procedure, an increase of 1 order of magnitude in response (from about 37 to 330) was obtained. Additionally, the response and recovery times were improved (by decreasing them from 58 and 61 s to 18 and 35 s, respectively). The calculated lowest detection limit of 200 ppb shows the excellent potential of the ZnO-T-CNT networks as NH3 vapor sensors. Room temperature operation of such networked ZnO-CNT hybrid tetrapods shows an excellent long-time stability of the fabricated sensors. Additionally, the gas-sensing mechanism was identified and elaborated based on the high porosity of the used three-dimensional networks and the excellent conductivity of the CNTs. On top of that, several single hybrid microtetrapod-based devices were fabricated (from samples with 2.0 wt % CNTs) with the help of the local metal deposition function of a focused ion beam/scanning electron microscopy instrument. The single microdevices are based on tetrapods with arms having a diameter of around 0.35 μm and show excellent NH3 sensing performance with a gas response (Igas/Iair) of 6.4. Thus, the fabricated functional networked ZnO-CNT hybrid tetrapods will allow to detect ammonia and to quantify its concentration in automotive, environmental monitoring, chemical industry, and medical diagnostics.

[1]  Oleg Lupan,et al.  Fabrication of ZnO nanorod-based hydrogen gas nanosensor , 2007, Microelectron. J..

[2]  Y. Weizmann,et al.  Sensory Arrays of Covalently Functionalized Single‐Walled Carbon Nanotubes for Explosive Detection , 2013 .

[3]  Arockia Jayalatha Kulandaisamy,et al.  Room temperature ammonia sensing properties of ZnO thin films grown by spray pyrolysis: Effect of Mg doping , 2016 .

[4]  Zhifu Liu,et al.  Room temperature gas sensing of p-type TeO2 nanowires , 2007 .

[5]  Eduard Llobet,et al.  Hybrid metal oxide and multiwall carbon nanotube films for low temperature gas sensing , 2007 .

[6]  M. Vaezi,et al.  Promoting effect of adding carbon nanotubes on sensing characteristics of ZnO hollow sphere-based gas sensors to detect volatile organic compounds , 2016 .

[7]  Ion Tiginyanu,et al.  Selective hydrogen gas nanosensor using individual ZnO nanowire with fast response at room temperature , 2010 .

[8]  Kong,et al.  Nanotube molecular wires as chemical sensors , 2000, Science.

[9]  Nam-Joon Cho,et al.  Flexible, Graphene‐Coated Biocomposite for Highly Sensitive, Real‐Time Molecular Detection , 2016 .

[10]  A. Mulchandani,et al.  Graphene nanomesh as highly sensitive chemiresistor gas sensor. , 2012, Analytical chemistry.

[11]  Niraj Sinha,et al.  Carbon nanotube-based sensors. , 2006, Journal of nanoscience and nanotechnology.

[12]  Oleg Lupan,et al.  A single ZnO tetrapod-based sensor , 2009 .

[13]  Koji Moriya,et al.  Indium oxide-based gas sensor for selective detection of CO , 1996 .

[14]  R. Adelung,et al.  Low powered, tunable and ultra-light aerographite sensor for climate relevant gas monitoring , 2016 .

[15]  Jin-Woo Han,et al.  A carbon nanotube based ammonia sensor on cotton textile , 2013 .

[16]  N. Du,et al.  Porous Indium Oxide Nanotubes: Layer‐by‐Layer Assembly on Carbon‐Nanotube Templates and Application for Room‐Temperature NH3 Gas Sensors , 2007 .

[17]  R. Adelung,et al.  Versatile Growth of Freestanding Orthorhombic α-Molybdenum Trioxide Nano- and Microstructures by Rapid Thermal Processing for Gas Nanosensors , 2014 .

[18]  Nguyen Duc Hoa,et al.  Preparing large-scale WO3 nanowire-like structure for high sensitivity NH3 gas sensor through a simple route , 2011 .

[19]  Jun Kameoka,et al.  Polymeric Nanowire Chemical Sensor , 2004 .

[20]  R. K. Bedi,et al.  Room-temperature ammonia sensor based on cationic surfactant-assisted nanocrystalline CuO. , 2010, ACS applied materials & interfaces.

[21]  Federica Rigoni,et al.  Enhancing the sensitivity of chemiresistor gas sensors based on pristine carbon nanotubes to detect low-ppb ammonia concentrations in the environment. , 2013, The Analyst.

[22]  Ashok Mulchandani,et al.  Single Polypyrrole Nanowire Ammonia Gas Sensor , 2007 .

[23]  Zheng Lou,et al.  Hybrid Co3O4/SnO2 Core-Shell Nanospheres as Real-Time Rapid-Response Sensors for Ammonia Gas. , 2016, ACS applied materials & interfaces.

[24]  S. Krupa Effects of atmospheric ammonia (NH3) on terrestrial vegetation: a review. , 2003, Environmental pollution.

[25]  T. Schenkel,et al.  Electron transport through single carbon nanotubes , 2007 .

[26]  K. Shimizu,et al.  Ammonia Sensing Mechanism of Tungstated-Zirconia Thick Film Sensor , 2007 .

[27]  A. Berg,et al.  Ammonia sensors and their applications - a review , 2005 .

[28]  R. Adelung,et al.  Synthesis, characterization and DFT studies of zinc-doped copper oxide nanocrystals for gas sensing applications , 2016 .

[29]  Shoushan Fan,et al.  Measuring the work function of carbon nanotubes with thermionic method. , 2008, Nano letters.

[30]  Nam-Joon Cho,et al.  Graphene‐Functionalized Natural Microcapsules: Modular Building Blocks for Ultrahigh Sensitivity Bioelectronic Platforms , 2016 .

[31]  J. H. Lee,et al.  Large-scale fabrication of highly sensitive SnO2 nanowire network gas sensors by single step vapor phase growth , 2012 .

[32]  Eduard Llobet,et al.  Boron- and nitrogen-doped multi-wall carbon nanotubes for gas detection , 2014 .

[33]  Junhong Chen,et al.  Room‐Temperature Gas Sensing Based on Electron Transfer between Discrete Tin Oxide Nanocrystals and Multiwalled Carbon Nanotubes , 2009 .

[34]  Nguyen Van Hieu,et al.  Size-dependent response of single-nanowire gas sensors , 2012 .

[35]  M. Weinert,et al.  Ag nanocrystal as a promoter for carbon nanotube-based room-temperature gas sensors. , 2012, Nanoscale.

[36]  Oleg Lupan,et al.  ighly sensitive and selective hydrogen single-nanowire nanosensor , 2012 .

[37]  R. Adelung,et al.  Enhanced ethanol vapour sensing performances of copper oxide nanocrystals with mixed phases , 2016 .

[38]  Martina Baum,et al.  Sacrificial Template Synthesis and Properties of 3D Hollow-Silicon Nano- and Microstructures. , 2016, ACS applied materials & interfaces.

[39]  Chen Liang,et al.  Field emission from zinc oxide nanowires , 2005 .

[40]  Deren Yang,et al.  Carbon Nanotube-ZnO Nanosphere Heterostructures: Low-Temperature Chemical Reaction Synthesis, Photoluminescence, and Their Application for Room Temperature NH 3 Gas Sensor , 2009 .

[41]  W. Benecke,et al.  Direct Growth of Freestanding ZnO Tetrapod Networks for Multifunctional Applications in Photocatalysis, UV Photodetection, and Gas Sensing. , 2015, ACS applied materials & interfaces.

[42]  T. Swager,et al.  Selective detection of ethylene gas using carbon nanotube-based devices: utility in determination of fruit ripeness. , 2012, Angewandte Chemie.

[43]  Alexander Star,et al.  Photoinduced charge transfer and acetone sensitivity of single-walled carbon nanotube-titanium dioxide hybrids. , 2013, Journal of the American Chemical Society.

[44]  S. Jo,et al.  Field emission of zinc oxide nanowires grown on carbon cloth , 2004 .

[45]  Jun Zhang,et al.  Polypyrrole-Coated SnO2 Hollow Spheres and Their Application for Ammonia Sensor , 2009 .

[46]  Y. Yoon,et al.  Highly Sensitive and Selective Gas Sensor Using Hydrophilic and Hydrophobic Graphenes , 2013, Scientific Reports.

[47]  Zheng Lou,et al.  Encapsuled nanoreactors (Au@SnO₂): a new sensing material for chemical sensors. , 2013, Nanoscale.

[48]  Peng Zhang,et al.  High photocatalytic activity of ZnO-carbon nanofiber heteroarchitectures. , 2011, ACS applied materials & interfaces.

[49]  R. Adelung,et al.  Multifunctional Materials: A Case Study of the Effects of Metal Doping on ZnO Tetrapods with Bismuth and Tin Oxides , 2017 .

[50]  Soo-Keun Lee,et al.  Gas sensors based on carbon nanoflake/tin oxide composites for ammonia detection. , 2014, Journal of hazardous materials.

[51]  R. Adelung,et al.  Multifunctional device based on ZnO:Fe nanostructured films with enhanced UV and ultra-fast ethanol vapour sensing , 2016 .

[52]  Joachim Goschnick,et al.  A gradient microarray electronic nose based on percolating SnO(2) nanowire sensing elements. , 2007, Nano letters.

[53]  R. Adelung,et al.  Non-planar nanoscale p–p heterojunctions formation in ZnxCu1−xOy nanocrystals by mixed phases for enhanced sensors , 2016 .

[54]  Kengo Shimanoe,et al.  Sensing properties of SnO2–Co3O4 composites to CO and H2 , 2004 .

[55]  D. A. Oudendag,et al.  The Manure Model: manure, minerals (N, P and K), ammonia emission, heavy metals and the use of fertiliser in Dutch agriculture , 1998 .

[56]  Oleg Lupan,et al.  Novel hydrogen gas sensor based on single ZnO nanorod , 2008 .

[57]  Rainer Adelung,et al.  Single and networked CuO nanowires for highly sensitive p‐type semiconductor gas sensor applications , 2016 .

[58]  Shun Mao,et al.  Modulating gas sensing properties of CuO nanowires through creation of discrete nanosized p-n junctions on their surfaces. , 2012, ACS applied materials & interfaces.

[59]  Won Il Park,et al.  Vertically aligned ZnO nanorods and graphene hybrid architectures for high-sensitive flexible gas sensors , 2011 .

[60]  Sebastian Wille,et al.  Rapid Fabrication Technique for Interpenetrated ZnO Nanotetrapod Networks for Fast UV Sensors , 2014, Advanced materials.

[61]  Zhimin Chen,et al.  Copper phthalocyanine noncovalent functionalized single-walled carbon nanotube with enhanced NH3 sensing performance , 2014 .

[62]  Yogendra Kumar Mishra,et al.  Aerographite: Ultra Lightweight, Flexible Nanowall, Carbon Microtube Material with Outstanding Mechanical Performance , 2012, Advanced materials.

[63]  M. Meyyappan,et al.  Carbon Nanotube Sensors for Gas and Organic Vapor Detection , 2003 .

[64]  Y. Mortazavi,et al.  Highly sensitive and selective sensors to volatile organic compounds using MWCNTs/SnO2 , 2012 .

[65]  Nguyen Van Hieu,et al.  Highly sensitive thin film NH3 gas sensor operating at room temperature based on SnO2/MWCNTs composite , 2008 .

[66]  Rainer Adelung,et al.  Silver-doped zinc oxide single nanowire multifunctional nanosensor with a significant enhancement in response , 2016 .

[67]  Gaurav Singh,et al.  ZnO decorated luminescent graphene as a potential gas sensor at room temperature , 2012, Carbon.

[68]  Gregory C. Rutledge,et al.  Spray‐Layer‐by‐Layer Carbon Nanotube/Electrospun Fiber Electrodes for Flexible Chemiresistive Sensor Applications , 2014 .