High-performance sulfur dioxide sensing properties of layer-by-layer self-assembled titania-modified graphene hybrid nanocomposite
Introduction
Sulfur dioxide (SO2) is one of major compounds of vehicle exhaust, as well as the main emissions of the thermal power plants and chemical production process [1], [2]. Moreover, SO2 gas is not only an environmental atmospheric pollutant, but it is also a hazardous gas having a human tolerance of about 5 ppm, which can bring to some serious diseases of human beings, such as respiratory, cardiovascular diseases and lung cancer [3], [4], [5]. Because of its toxicity to human health and environmental contamination, trace detection of SO2 gas has attracted considerable attention. Up to now, many methods and instruments such as spectroscopy and solid-state electrochemistry techniques have been developed for SO2 detection, but they are expensive and cumbersome [6], [7], [8]. Recently, metal-oxide semiconducting (MOS) materials such as SnO2 [9], ZnO [10], TiO2 [3], [6], [11] and WO3 [12], were extensively employed for constructing SO2 gas sensor. Among them, TiO2 has been widely investigated for gas sensing due to its unique physicochemical properties, it suffers from high operating temperature (200–400 °C), resulting in high power consumption and difficulty in integration [13], [14]. Therefore, exploring a novel sensing material and method toward SO2 detection at room temperature is highly desired.
Graphene, a two-dimensional monolayer of graphite sheet consisting of sp2 hybridized carbon atoms, has attracted the attention of gas sensing community owing to its unique nanostructure, excellent physical and chemical properties [15], [16], [17]. Graphene-based nanostructures have been extensively used to detect several gas species at extremely low concentrations, even down to the single molecule level at room temperature, which can be ascribed to the unprecedented electronic conductivity, high specific surface area, ultra-small thickness, extremely low-noise characteristics and high thermal stability [18], [19]. Among graphene derivatives, graphene oxide (GO) and reduced graphene oxide (rGO) have triggered recently tremendous attention due to their facile preparation and novel applications [20]. Although great potentials have reported on graphene, its sensitivity to gas species detection is limited. Shao et al. has revealed that intrinsic graphene is not an efficient material towards SO2 by using first-principles approach based on the spin-polarized density functional theory [21]. Notably, metal oxide-decorated graphene is emerging as a class of candidate materials to construct high-performance gas sensors towards various gas species, such as ethanol, acetone, NO2, NH3 and H2S [22], [23], [24], [25], [26]. Ren et al. fabricated a SO2 gas sensor with CVD grown graphene configured in a field effect transistor (FET) device, and its sensing properties at a SO2 concentration of 50 ppm was exhibited [27]. Furthermore, at least to our knowledge, the SO2 gas sensor based on metal oxide-decorated graphene hybrid film has not been reported till now.
In this work, we presented a novel ppb-level SO2 gas sensor based on TiO2/rGO composite film, which was fabricated by using layer-by-layer (LbL) self-assembly technique and facile thermal reduction. The hierarchical nanostructure of TiO2/rGO thin film was fabricated on the substrate with interdigital microelectrodes. The resulting TiO2/rGO hybrid film was characterized by using SEM, TEM, XRD, EDS and Raman spectroscopy. The sensing properties of the presented SO2 sensor were investigated by exposing to ultralow-concentration of SO2 ranging from 1 ppb to 5 ppm at room temperature. As a result, the sensor achieved ppb-level detection, fast response-recovery characteristics, good selectivity and long-term stability towards SO2 at room temperature.
Section snippets
Materials
Urea (≥99%) and Ti(SO4)2 (≥96%) were offered by Sinopharm Chemical Reagent Co. Ltd. The high-purity graphene oxide (GO) suspension was supplied by Chengdu Organic Chemicals Co. Ltd (Chengdu, China). Polycation and polyanion used for LbL assembly were 1.5 wt% PDDA (Sigma-Aldrich) and 0.3 wt% PSS (Sigma-Aldrich) with 0.5 M NaCl in both for ionic strength.
Sensor fabrication
The typical process for manufacturing the sensor device is shown in Fig. 1. A Cu/Ni layer with thickness of 20 μm was first deposited on PCB
Sample characterization
The SEM surface images of TiO2, rGO, self-assembled TiO2/rGO samples and cross-sectional image of multi-layer TiO2/rGO film are shown in Fig. 3. Fig. 3(a) shows as-synthesized TiO2 sample has nanosphere shape with a diameter around 10 nm, and Fig. 3(b) shows that the rGO film has wrinkles which overlap at the edges, and also exhibits randomly aggregated morphology as typical feature for rGO. Fig. 3(c) shows the SEM image of TiO2/rGO nanostructure, rGO flakes are wrapped on the TiO2 nanosphere
Conclusions
A high-performance room-temperature SO2 gas sensor based on TiO2/rGO nanocomposite was presented in this paper. The sensor was fabricated by combining hydrothermal route with layer-by-layer self-assembly technology. The sensing properties of the presented sensor were investigated upon exposure to SO2 gas. The observed results showed the sensor has high response to SO2 gas, fast response and recovery time, good reversibility and repeatability toward low concentration detection at room
Acknowledgements
This work was supported by the National Natural Science Foundation of China (No. 51407200, 51405257), the Science and Technology Plan Project of Shandong Province (No. 2014GSF117035), the Fundamental Research Funds for the Central Universities of China (No. 15CX05041A), and the Science and Technology Development Plan Project of Qingdao, China (No. 16-6-2-53-nsh).
Dongzhi Zhang received his B.S. degree from Shandong University of Technology in 2004, M.S. degree from China University of Petroleum in 2007, and obtained Ph.D. degree from South China University of Technology in 2011. He is currently an associate professor at China University of Petroleum (East China), Qingdao, China. His fields of interests are precision measurement technology and instruments, MEMS sensors fabrication and their application.
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Dongzhi Zhang received his B.S. degree from Shandong University of Technology in 2004, M.S. degree from China University of Petroleum in 2007, and obtained Ph.D. degree from South China University of Technology in 2011. He is currently an associate professor at China University of Petroleum (East China), Qingdao, China. His fields of interests are precision measurement technology and instruments, MEMS sensors fabrication and their application.
Jingjing Liu received her B.S. degree from Pingdianshan University in 2013, M.S. degree from China University of Petroleum (East China) in 2016. Her fields of interests include carbon nanomaterials-based gas sensors, precision measurement technology and instruments.
Chuanxing Jiang received her B.S. degree in automation from Yantai University in 2015. Currently, she is a graduate student at China University of Petroleum (East China), Qingdao, China. Her fields of interests include 2D nanomaterials-based gas sensors, precision measurement technology and instruments.
Peng Li received B.S. degree in Electronic Engineering from Tianjin University, China, in 2007, and Ph. D. degree in Precision Instruments from Tsinghua University, China, in 2012. He is currently working in Department of Mechanical engineering at Tsinghua University. His current research interests include graphene material synthesis, and graphene NEMS device fabrication and their application in actuators and sensors.
Yan’e Sun received her B.S. degree in measurement & control technology and instrumentation from Ludong University in 2014. Currently, she is a graduate student at China University of Petroleum (East China), Qingdao, China. Her fields of interests include carbon nanomaterials-based gas sensors, precision measurement technology and instruments.