Hierarchical Assembly of α-Fe2O3 Nanorods on Multiwall Carbon Nanotubes as a High-Performance Sensing Material for Gas Sensors.

This paper presents a facile hydrolysis reaction and annealing for preparing a novel hierarchical nanoheterostructure via assembly of α-Fe2O3 nanorods onto multiwall carbon nanotubes (MWCNTs) backbones. The as-synthesized nanocomposites were characterized using XRD (X-ray diffraction), FESEM (Field emission scanning electron microscopy), TEM (Transmission electron microscopy), XPS (X-ray photoelectron spectroscopy) and BET (Surface Area and Porosity System). The observations showed uniform α-Fe2O3 nanorods approximately 100-200 nm in length and 50-100 nm in diameter that were hierarchically assembled onto the surface of the MWCNTs. The formation of the heterostructure was investigated by observing the evolution of the microstructure of the products at different reaction times. The X-ray photoelectron spectra (XPS) showed that the ability of the absorbing oxygen was enhanced by the formation of the heterostructure composites. Moreover, as a proof-of-concept presentation, the novel CNTs@α-Fe2O3 hierarchical heterostructure acted as a gas sensitive material. Significantly, the composites exhibited excellent sensing properties for acetone with high sensitivity, exceptional selectivity and good reproducibility. The response of the CNTs@α-Fe2O3 sensor to 100 ppm acetones at 225 °C was nearly 35, which was superior to the single α-Fe2O3 nanorods with a response of 16, and the detection limit of the sensor was 500 ppb. The enhanced properties were mainly attributed to the unique structure and p-n heterojunction between the CNTs and the α-Fe2O3 nanorods.

[1]  Zhengwei Pan,et al.  Work function at the tips of multiwalled carbon nanotubes , 2001 .

[2]  Peng Sun,et al.  Hierarchical α-Fe2O3/SnO2 semiconductor composites: Hydrothermal synthesis and gas sensing properties , 2013 .

[3]  Buxing Han,et al.  Synthesis of ZrO2-carbon nanotube composites and their application as chemiluminescent sensor material for ethanol. , 2006, The journal of physical chemistry. B.

[4]  Jiajun Chen,et al.  Growth of monoclinic WO3nanowire array for highly sensitive NO2 detection , 2009 .

[5]  Jin Li,et al.  Multilayered ZnO Nanosheets with 3D Porous Architectures: Synthesis and Gas Sensing Application , 2010 .

[6]  F. Huang,et al.  Hydrothermal synthesis, structural characteristics, and enhanced photocatalysis of SnO(2)/alpha-Fe(2)O(3) semiconductor nanoheterostructures. , 2010, ACS nano.

[7]  N. Yamazoe New approaches for improving semiconductor gas sensors , 1991 .

[8]  R. N. Karekar,et al.  Formulation and characterization of ZnO:Sb thick-film gas sensors , 1998 .

[9]  Eduard Llobet,et al.  Au nanoparticle-functionalised WO3 nanoneedles and their application in high sensitivity gas sensor devices. , 2011, Chemical communications.

[10]  Riichiro Saito,et al.  Raman spectroscopy of carbon nanotubes , 2005 .

[11]  Bin Xu,et al.  Functional hybrid materials based on carbon nanotubes and metal oxides , 2010 .

[12]  Junhong Chen,et al.  Nanocarbon-based gas sensors: progress and challenges , 2014 .

[13]  Dianzeng Jia,et al.  Low-heating solid-state synthesis and excellent gas-sensing properties of α-Fe2O3 nanoparticles , 2013 .

[14]  G. Lu,et al.  Humidity-sensing properties of urchinlike CuO nanostructures modified by reduced graphene oxide. , 2014, ACS applied materials & interfaces.

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

[16]  Chao‐Nan Xu,et al.  Room temperature sensing of ozone by transparent p-type semiconductor CuAlO2 , 2004 .

[17]  A. Gurlo,et al.  Nanosensors: towards morphological control of gas sensing activity. SnO2, In2O3, ZnO and WO3 case studies. , 2011, Nanoscale.

[18]  John Parthenios,et al.  Chemical oxidation of multiwalled carbon nanotubes , 2008 .

[19]  Thorsten Wagner,et al.  Ordered Mesoporous In2O3: Synthesis by Structure Replication and Application as a Methane Gas Sensor , 2009 .

[20]  H. Salavagione,et al.  Chemical sensors based on polymer composites with carbon nanotubes and graphene: the role of the polymer , 2014 .

[21]  Zeng Wen,et al.  Gas-sensing properties of SnO2–TiO2-based sensor for volatile organic compound gas and its sensing mechanism , 2010 .

[22]  M. Cao,et al.  Porous Fe3O4/Carbon Core/Shell Nanorods: Synthesis and Electromagnetic Properties , 2009 .

[23]  Younan Xia,et al.  A Solution-Phase, Precursor Route to Polycrystalline SnO2 Nanowires That Can Be Used for Gas Sensing under Ambient Conditions. , 2004 .

[24]  S. Phanichphant,et al.  Semiconducting metal oxides as sensors for environmentally hazardous gases , 2011 .

[25]  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.

[26]  M. Sheikhi,et al.  Highly sensitive wireless H2S gas sensors at room temperature based on CuO-SWCNT hybrid nanomaterials , 2016 .

[27]  Haojie Song,et al.  Hydrothermal synthesis, growth mechanism and gas sensing properties of Zn-doped α-Fe2O3 microcubes , 2015 .

[28]  V. Idakiev,et al.  Au/α-Fe2O3 catalyst for water–gas shift reaction prepared by deposition–precipitation , 1998 .

[29]  Yan Li,et al.  Hydrothermal synthesis of MnO2 nanowires: structural characterizations, optical and magnetic properties , 2014 .

[30]  G. Morell,et al.  Room temperature gas sensor based on tin dioxide-carbon nanotubes composite films , 2014 .

[31]  Xiaofei Yang,et al.  Flexible morphology-controlled synthesis of monodisperse α-Fe2O3 hierarchical hollow microspheres and their gas-sensing properties , 2012 .

[32]  Michele Penza,et al.  Functional characterization of carbon nanotube networked films functionalized with tuned loading of Au nanoclusters for gas sensing applications , 2009 .

[33]  N. Yamazoe,et al.  Oxide Semiconductor Gas Sensors , 2003 .

[34]  David E. Williams Semiconducting oxides as gas-sensitive resistors , 1999 .

[35]  Y. Shimizu,et al.  Variations in I-V characteristics of oxide semiconductors induced by oxidizing gases , 1996 .

[36]  Peng Sun,et al.  Hydrothermal synthesis of 3D urchin-like α-Fe2O3 nanostructure for gas sensor , 2012 .

[37]  D. Schroder Semiconductor Material and Device Characterization , 1990 .

[38]  Qingyi Pan,et al.  The template-free synthesis of square-shaped SnO2 nanowires: the temperature effect and acetone gas sensors , 2008, Nanotechnology.

[39]  Hailong Yu,et al.  Synthesis and H2S gas sensing properties of cage-like α-MoO3/ZnO composite , 2012 .

[40]  Feng Liu,et al.  Fabrication and gas sensing properties of hollow core–shell SnO2/α-Fe2O3 heterogeneous structures , 2014 .

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

[42]  N. Yamazoe,et al.  Hierarchical α-Fe2O3/NiO composites with a hollow structure for a gas sensor. , 2014, ACS applied materials & interfaces.

[43]  Sunghoon Park,et al.  Enhanced acetone gas sensing performance of the multiple-networked Fe2O3-functionalized In2O3 nanowire sensor , 2015 .

[44]  H. Kataura,et al.  Electrochemical tuning of electronic states in single-wall carbon nanotubes studied by in situ absorption spectroscopy and ac resistance , 2001 .

[45]  D. Cann,et al.  Response kinetics of doped CuO/ZnO heterocontacts. , 2005, The journal of physical chemistry. B.