Next Article in Journal
Magnetic Cell Centrifuge Platform Performance Study with Different Microsieve Pore Geometries
Previous Article in Journal
PDMAC: A Priority-Based Enhanced TDMA Protocol for Warning Message Dissemination in VANETs
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Sensors
Volume 20
Issue 1
10.3390/s20010046
sensors-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Preparation and NH3 Gas-Sensing Properties of Double-Shelled Hollow ZnTiO3 Microrods

by
Pi-Guey Su
* and
Xiang-Hong Liu
Department of Chemistry, Chinese Culture University, Taipei 111, Taiwan
*
Author to whom correspondence should be addressed.
Sensors 2020, 20(1), 46; https://doi.org/10.3390/s20010046
Submission received: 12 November 2019 / Revised: 15 December 2019 / Accepted: 17 December 2019 / Published: 19 December 2019
(This article belongs to the Section Chemical Sensors)
Browse Figures
Review Reports Versions Notes

Abstract

:
A novel double-shelled hollow (DSH) structure of ZnTiO3 microrods was prepared by self-templating route with the assistance of poly(diallyldimethylammonium chloride) (PDDA) in an ethylene glycol (EG) solution, which was followed by calcining. Moreover, the NH3 gas-sensing properties of the DSH ZnTiO3 microrods were studied at room temperature. The morphology and composition of DSH ZnTiO3 microrods films were analyzed using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The formation process of double-shelled hollow microrods was discussed in detail. The comparative gas-sensing results revealed that the DSH ZnTiO3 microrods had a higher response to NH3 gas at room temperature than those of the TiO2 solid microrods and DSH ZnTiO3 microrods did in the dark. More importantly, the DSH ZnTiO3 microrods exhibited a strong response to low concentrations of NH3 gas at room temperature.

1. Introduction

ZnO and TiO2 films have been extensively studied for use in sensing, but traditional ZnO and TiO2 gas sensors, which are based on ZnO and TiO2 films, can typically only be used at temperatures from 300 to 500 °C [1,2]. Additionally, selectivity is also an important property of metal oxide-based sensors. Several designs of sensors’ construction were proposed for achieving the selectivity of these sensors, such as directly doping small amounts of noble metals (Au, Pd, and Pt), a suitable filter containing the noble metal catalysts method, and nano-carbon-based composite materials film [3,4,5,6]. ZnO and TiO2 are well known inorganic photocatalysts, so that ultra-violet (UV) irradiation has been used to reduce the operating temperature of these sensors [7,8,9,10]. ZnO–TiO2 binary oxide systems have a better photocatalytic performance than single systems [11]. The ZnO-TiO2 binary oxide system had three compounds: they are ZnTiO3 (cubic, hexagonal), Zn2TiO4 (cubic, tetragonal) and Zn2Ti3O8 (cubic) [12,13,14,15,16,17,18]. ZnTiO3 has attracted particular interest because of its potential for use in the photocatalysis of the degradation of organic pollutants, and in adsorption and microwave devices [18,19,20]. Numerous reports have revealed that ZnTiO3 has favorable photocatalytic properties in visible light [21,22,23,24], favoring its use for gas sensors at room temperature [25]. Yadav et al. [25] fabricated a ZnTiO3 nanopowders film using a physicochemical method for sensing liquefied petroleum gas (LPG) at room temperature. Ippolito et al. [26] fabricated an acetone gas sensor that was made of ZnTiO3 nanoarrays using a hydrothermal method. The limit of detection (LOD) of this sensor under light and at 350 °C was 10 ppb.
One-dimensional (1D) nanostructured materials such as tubes, wires, belts, and rods have great potential for use in gas sensors, not only because of their excellent optical, electrical, and mechanical properties, but also because of their efficiency and activity sites, which are caused by their high porosity and large surface area [18,27]. Hollow micro/nanostructures have also attracted enormous interest because of their many hollow cavities, which make the surface area of hollow structures significantly greater than that of their solid counterparts [28]. In recent decades, many methods have been used to prepare ZnTiO3 nanopowders, such as the conventional solid-state reaction, the molten salt method, the sol-gel method, the chemical bath deposition and the hydrothermal method [13,14,15,16,29,30,31]. The physicochemical properties of ZnTiO3 nanopowders depend on their morphology, the size of the crystallites, and the crystallographic structure. Recently, Chi et al. [18] fabricated pristine solid ZnTiO3 microrods, and You et al. [32] fabricated a reduced grapheme oxide decorated solid ZnTiO3 microrod composite using the polyvinylpyrrolidone (PVP)-assisted sol-gel method for use in the photo-degradation of rhodamine B. However, no attempt has been made to prepare a double-shelled hollow (DSH) structure of ZnTiO3 microrods and to study their NH3 gas-sensing properties at room temperature.
Ammonia (NH3) is known to be highly hazardous to the environment and the human body because of its high toxicity. Accordingly, the fabrication of NH3 gas sensors that can be used at room temperature, with a high response and a low production cost, has attracted much attention. In this work, a novel room-temperature NH3 gas sensor with a high sensitivity, based on novel DSH ZnTiO3 microrods, was fabricated. DSH ZnTiO3 microrods were prepared using a self-templating approach, by heating sol-gel derived Zn-Ti glycolates with poly(diallyldimethylammonium chloride) (PDDA) in an ethylene glycol (EG) solution and then calcining. This method is very simple, has a low production, and does not involve heterogeneous coating, so it can be easily scaled up for the fabrication of sensors. A plausible process for the fabrication of DSH structures is proposed. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), and energy dispersive X-ray (EDX) analysis were used to characterize the composition and morphologies of the DSH ZnTiO3 microrods. The NH3-sensing properties of DSH ZnTiO3 microrods at room temperature, including the sensing response, sensing linearity, selectivity, response/recovery times, repeatability, stability, and sensing mechanism, were also studied.

2. Experimental Methods

2.1. Materials

The following chemicals were used as received without further purification: titanium (IV)-ethylhexanoate (Ti[(OOCCH(CH2)4(CH3)2)]4 (TE, Alfa Aesar), zinc acetate dehydrate (Zn(OAc)2·2H2O; Sigma-Aldrich, St. Louis, MO, USA), ethylene glycol (EG, J. T. Baker), poly (diallyldimethylammonium chloride (PDDA, molecular weight (Mw) = 200,000~350,000, Aldrich).

2.2. Fabrication of Gas Sensors Based on DSH ZnTiO3 Microrods and Measurement of Their Sensing Properties

1.25 g TE, 0.25 g Zn(OAc)2·2H2O and 0.3 mL PDDA were added to a 10 g EG solution, which was then stirred at 190 °C for 1.5 h. An as-prepared precursor solution (PDDA-Zn-Ti-glycolates rods precursor) was drop-coated on an alumina substrate with interdigitated electrodes (IDE). The system was then calcined at 500 °C for 4 h at a heating rate of 5 °C min−1 for decomposing the matrix polymer and organic groups, and for oxidizing and crystallizing the Zn-Ti-glycolates. Figure 1a shows a picture of the structure of the as-prepared NH3 gas sensors. The preparation and characterizations of the TiO2 solid microrods were completed according to our previous report [33].
The electrical and NH3 gas-sensing characteristics of the DSH ZnTiO3 microrods were measured using a bench system, as shown in Figure 1b. The volume of the bench system is 18 L. A Direct current (DC) mode was used to measure the resistance of the as-prepared sensors. A power supply (GW, PST-3202) applied a fixed 5 V to the sensor circuit. A DAQ device (NI, USB-6218) was used to measure the resistance of the sensor in various concentrations of NH3 gas. A standard 1000 ppm NH3 gas in N2 gas (Shen Yi Gas Co., Taiwan) was used to prepare the required various NH3 gas concentrations. The desired various gas concentrations were prepared by diluting the known volume of standard NH3 gas with dry air, and were calibrated by a standard gas sensor system (Dräger, MiniWarn). A fan was used to disperse the testing gases inside the bench system and was purged with air. All experiments were measured at room temperature (about 23.0 ± 1.5 °C) and the relative humidity at 45% RH. The response (S) of the sensors was calculated according to Equation (1):
S   ( % ) = ( R air − R gas ) R air × 100 % .
Rair and Rgas are the electrical resistances of the sensor in the air and testing gas at the exposure time of 300 s, respectively.

2.3. Characterization of DSH ZnTiO3 Microrods

The composition and morphologies of the DSH ZnTiO3 microrods film coated on an alumina substrate were investigated using X-ray diffraction (XRD) using Cu Kα radiation (Shimadzu, Lab XRD-6000), scanning electron microscope (SEM, JEOL JSM-5310), transmission electron microscopy (TEM, JEM-1400; JEOL, Tokyo, Japan), selected-area electron diffraction (SAED) and energy dispersive X-ray (EDX) analysis.

3. Results and Discussion

3.1. Characteristics of DSH ZnTiO3 Microrod Film

3.1.1. XRD Characterization of DSH ZnTiO3 Microrods

Figure 2a,b presents the XRD spectra of the DSH ZnTiO3 microrods that were calcined at 500 °C for 4 h and without calcining, respectively. The reflections at (220), (311), (400), (511) and (440) agree closely with the cubic crystal phase of ZnTiO3. No peak that corresponded to the TiO2, ZnO or zinc titanates, all of which are associated with other stoichiometries, was observed. These results are consistent with the literature [18,32]. The XRD results further verified that the formation and crystallinity of the as-prepared ZnTiO3 at temperatures as low as 500 °C were attributable mainly to the short diffusion paths of metal ions during the heat treatment of the PDDA-Zn-Ti-glycolates rods as the precursor in the polyol processing [14]. Additionally, the diffraction peaks of the DSH ZnTiO3 microrods without calcining were unobvious and broad, indicating a poor crystalline structure (Figure 2b).

3.1.2. SEM and TEM Analyses of Morphology of DSH ZnTiO3 Microrod Film

Figure 3 presents the SEM images of the partially DSH ZnTiO3 microrod film that was prepared by the self-templating approach, which was followed by calcining. Figure 3a reveals the presence of clearly regular microrods, which had aggregated into bundles. The high-magnification SEM image of the DSH ZnTiO3 microrods (Figure 3b) shows that the microrods were linked together in an interconnected porous network structure. The length and diameter of the DSH ZnTiO3 microrods were about 3~6 μm and 0.25~0.45 μm, respectively. The microrod structure had round and narrow tips and open ends (indicated by arrows). Figure 4 presents the TEM images of the DSH ZnTiO3 microrods that were synthesized by PDDA-assisted self-templating. The low-magnification TEM image of a single DSH ZnTiO3 microrod (Figure 4a) shows a partially hollow structure at its end. The higher-magnification TEM image of the selected area in Figure 4a indicates that the ZnTiO3 microrods had a double-shelled structure (indicated by arrows) (Figure 4b). The shell was thin, and the internal diameter of the hollow rod was about 0.23 μm. The high-resolution TEM (HRTEM) image of the DSH ZnTiO3 microrods indicates that the lattice spacing of the adjacent lattice planes was about 0.27 nm, consistent with the (220) crystal plane of cubic ZnTiO3 (Figure 4c). The SAED pattern (inset in Figure 4c) confirms that the microrods comprised cubic ZnTiO3, consistent with the relevant XRD results. To further investigate the composition of the DSH ZnTiO3 microrods, EDX elemental mapping and an elemental analysis (Figure 4e) were conducted. The EDX elemental mapping (Figure 4d) suggested the presence of Zn, Ti, and O only in the DSH ZnTiO3 microrods. The EDX elemental analysis (Figure 4e) revealed an atomic ratio of Zn to Ti of close to 1:1, revealing a close match with the stoichiometric composition.
Figure 5 presents a plausible synthesis of the DSH ZnTiO3 microrods. First, chain-like sol-gel-derived Zn-Ti-glycolates were formed by heating in an EG solution. EG is well known to serve as a complexing agent in the formation of Zn-glycolate and Ti-glycolate from Zn2+ and Ti4+ ions (path (1)) [34], respectively. The Zn-glycolate was then intercalated with Ti-glycolate, forming chain-like Zn-Ti-glycolates, similar to those described elsewhere [34,35,36]. Then (path (2)), during the sol-gel process, PDDA was adsorbed on the surface of these chain-like Zn-Ti-glycolates by electrostatic attraction at a high temperature, forming hollow PDDA-Zn-Ti-glycolates rods as a precursor. In the cooperative assembly process, PDDA exhibited the dual action of protecting and etching. PDDA molecules were wrapped outside the chain-like Zn-Ti-glycolates in the initial stage of heating, protecting them in a stable shell. Since the PDDA (with quaternary amines) was coated on the surfaces of chain-like Zn-Ti-glycolates, the increase in the amount of counterions (OH−) nearby increased the local alkalinity and facilitated etching accordingly. Hollow PDDA-Zn-Ti-glycolates rods were thus formed as a precursor [28,37]. Additionally, if many of the surface Zn-Ti-glycolates rods became covered by PDDA, the penetration of etching species into the interior of the Zn-Ti-glycolates rods was prevented, and no hollow structure was formed. Finally (path (3)), the hollow PDDA-Zn-Ti-glycolates rods as the precursor underwent a post-calcination treatment at a high heating rate (5 °C min−1). The outmost PDDA-Zn-Ti-glycolates layer with a limited thickness was concentrated; the outermost ZnTiO3 shell was degraded and oxidized; and the inner PDDA-Zn-Ti-glycolates layer was contracted. Thereafter, the outermost ZnTiO3 shell separated from the shrinking internal PDDA-Zn-Ti-glycolates layer. Subsequently, the inner ZnTiO3 shell formed in the same way until the organic groups in the precursor PDDA-Zn-Ti-glycolates burned out [38]. As a result, DSH ZnTiO3 microrods were formed.

3.2. NH3 Gas-Sensing Properties of DSH ZnTiO3 Microrod Film

Figure 6 presents the responses (S) of the TiO2 solid microrods, ZnTiO3 powders, DSH ZnTiO3 microrods, and DSH ZnTiO3 microrods in the dark, to 100 ppm of NH3 gas at room temperature. The response (S) values for the TiO2 solid microrods, ZnTiO3 powders, DSH ZnTiO3 microrods, and DSH ZnTiO3 microrods in the dark were 16.17, 17.75, 45.32, and 21.07, respectively. The DSH ZnTiO3 microrods exhibited a stronger response (S) than those of the TiO2 solid microrods and ZnTiO3 powders, and the DSH ZnTiO3 microrods in the dark. This result may be attributable to the fact that the DSH ZnTiO3 microrods exhibited a higher surface area, larger pores, and a greater total pore volume than the TiO2 solid microrods and ZnTiO3 powders did. Moreover, the fact that ZnTiO3 exhibited a higher response in the visible light than in the dark may be attributable to the fact that the DSH ZnTiO3 microrods had a good photocatalytic activity in the visible light [39,40]. Figure 7a presents the dynamic responses (S) of the DSH ZnTiO3 microrods to various concentrations of NH3. They exhibited a response (S) of 5.1%, even to a low NH3 testing concentration of 1 ppm. The limit of detection (LOD) was estimated at the lower calibration point of 1 ppm by considering a S/N of 3. The LOD was 0.45 ppm. Figure 7b presents the linear dependence of the response (S) of the DSH ZnTiO3 microrods on the concentration of NH3 gas. The sensitivity ( Δ S Δ C ) is obtained from the slope of the linear sensing curve. The linear sensing properties in the ranges of 1 to 20 ppm and 20 to 200 ppm of NH3 gas differed. The sensitivity at 5 to 150 ppm of NH3 gas was larger than that at 150 to 300 ppm, and a rapid decrease in the slope was observed from 20 to 200 ppm of the NH3 gas. This result was related to the synergistic effect of the surface area and the photocatalytic activity of the DSH ZnTiO3 microrods. As the concentration of NH3 increased to 20~200 ppm, the number of active sites for adsorption decreased, causing a rapid decline in the slope. Figure 8 plots the real-time resistance of the DSH ZnTiO3 microrods to 5 ppm of NH3 over time. The response time (ResT90) and recovery (RecT90) times are calculated as the time taken for the resistance of the sensor to change by 90% of its maximum change after the exposing time of the NH3 gas at 300 s. The response (ResT90) and recovery (RecT90) times of the DSH ZnTiO3 microrods were 93 and 363 s, respectively. Figure 9 plots the response and recovery times as a function of the NH3 gas concentration. The recovery time increased with an increasing NH3 gas concentration. The rather long recovery time was attributable to the hollow interior cavities of the DSH ZnTiO3 microrods. The sensor also exhibited a good reversibility. Figure 10 plots the effect of the ambient humidity on the response (S) of the DSH ZnTiO3 microrods. The response (S) of the DSH ZnTiO3 microrods decreased with an increase in the ambient humidity, with measurements at testing concentrations of NH3 of 5 ppm. This result was reasonable because the physisorbed water occupied the active sites of the DSH ZnTiO3 microrods. Figure 11 plots the results concerning the interfering effects of CO, H2, NO2, NO, and SO2 gases on the DSH ZnTiO3 microrods. These interfering gases may be regarded as having unobvious interference effects with NH3 at 100 ppm. However, NO2 and NO gases detectably interfered with NH3 at less than 5 ppm. Figure 12 plots the long-term stability of the DSH ZnTiO3 microrods. The mean response (S) of the DSH ZnTiO3 microrods to 50 ppm and 5 ppm NH3 gas for 68 days were 49.11 and 17.34, respectively. The response drift for 68 days was calculated as the relative standard deviation (RSD). The RSD for the DSH ZnTiO3 microrods to 50 ppm and 5 ppm NH3 gas were 6.5% and 8.3%, respectively. The relative standard deviation (RSD) of the response (S) of the DSH ZnTiO3 microrods to 50 ppm NH3 gas was 6.0%, indicating its favorable repeatability. The NH3 gas-sensing properties of the presented NH3 sensor was compared with those of sensors in the literature, as shown in Table 1 [41,42,43,44,45,46]. The DSH ZnTiO3 microrods had the lowest detection limit for sensing NH3 gas at room temperature.

3.3. Electrical Properties and NH3 Gas-Sensing Mechanism of DSH ZnTiO3 Microrod Film

Figure 13 plots the real-time resistance of the DSH ZnTiO3 microrod film as a function of time for various concentrations of NH3. The resistance of the DSH ZnTiO3 microrod film herein was reduced by exposure to NH3 gas (electron-donating). Accordingly, the prepared DSH ZnTiO3 microrod film had the electrical property of an n-type semiconductor. Therefore, the changes in resistance of the DSH ZnTiO3 microrod film by exposure to NH3 gas have been suggested from the reports of Hieu et al. [47], Gupta et al. [48], and Shi et al. [49], as illustrated in Equations (2)–(4) [47,48,49]:
O2 (g) + e− O2 (ads),
NH3(g) NH3(ads),
4 NH3(ads) + 3 O2 (ads)− 2 N2 + 6 H2O + 6 e−.
First, the atmospheric oxygen adsorbed electrons from the conduction band of the surface of the DSH ZnTiO3 microrod film, forming O2(ads)− (Equation (2)). Then, the adsorption of electron-donating NH3 gas molecules interacts with pre-adsorbed oxygen ions (O2(ads)−) and releases electron carriers into the n-type DSH ZnTiO3 microrod film, causing its electrical resistance to decrease, while increasing the concentration of NH3 gas (Equations (3) and (4)). From all of the above, two main effects are proposed to explain why the DSH ZnTiO3 microrod film had the strongest response (S). First, the DSH ZnTiO3 microrods had hollow cavities, and their consequently large surface area favored NH3 gas adsorption. Second, the fact that the response of the DSH ZnTiO3 microrod film in light was stronger than in the dark is directly related to its photocatalytic activity. In the presence of sunlight, electrons were photo-excited from the valence band to the conduction band of the DSH ZnTiO3 microrods, and these photo-generated electrons at the surface of the DSH ZnTiO3 microrods were then transferred to the adsorbed oxygen, increasing the adsorbed oxygen ions, favoring the chemisorption of NH3, and thereby improving the response of the DSH ZnTiO3 microrods [28,29,33,34].

4. Conclusions

Novel DSH structures of ZnTiO3 microrods were fabricated via a PDDA-assisted self-templating approach in an EG solution and were then calcined. The synergistic surface-protecting and core-etching of chain-like Zn-Ti-glycolates by PDDA explains the formation of double-shelled hollow structures of the ZnTiO3 microrods. The ZnTiO3 microrods exhibited a strong response to low concentrations of NH3 gas at room temperature, including a good sensitivity (5.1%) at 1 ppm NH3, a good linearity (Y = 1.5575 X + 7.5526; R2 = 0.9068) at 1~20 ppm NH3, a fast response time (93 s), a good repeatability, a good reversibility, a high selectivity, and a good long-term stability (at least 68 days).

Author Contributions

Conceptualization, P.-G.S.; Methodology, P.-G.S.; Investigation, P.-G.S. and X.-H.L.; Writing—original draft preparation, P.-G.S.; Writing—review and editing, P.-G.S.; Supervision, P.-G.S.; Project administration, P.-G.S.; Funding acquisition, P.-G.S. All authors have read and agreed to the published version of the manuscript.

Funding

This research was founded by Ministry of Science and Technology of Taiwan, grant no. MOST 108-2113-M-034-003.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Zhu, L.; Zeng, W. Room-temperature gas sensing of ZnO-based gas sensor: A review. Sens. Actuators A 2017, 267, 242–261. [Google Scholar] [CrossRef]
  2. Dey, A. Semiconductor metal oxide gas sensors: A review. Mater. Sci. Eng. B 2018, 229, 206–217. [Google Scholar] [CrossRef]
  3. Joshi, N.; Hayasaka, T.; Liu, Y.; Liu, H.; Oliveira, O.N., Jr.; Lin, L. A review on chemiresistive room temperature gas sensors based on metal oxide nanostructures, graphene and 2D transition metal dichalcogenides. Microchim. Acta 2018, 185, 213–229. [Google Scholar] [CrossRef] [PubMed]
  4. Xia, Y.; Li, R.; Chen, R.; Wang, J.; Xiang, L. 3D architectured graphene/metal oxide hybrids for gas sensors: A review. Sensors 2018, 18, 1456. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  5. Sharma, B.; Sharma, A.; Kim, J.S. Recent advances on H2 sensor technologies based on MOX and FET devices: A review. Sens. Actuators B 2018, 262, 758–770. [Google Scholar] [CrossRef]
  6. Nazemi, H.; Joseph, A.; Park, J.; Emadi, A. Advanced micro- and nano-gas sensor technology: A review. Sensors 2019, 19, 1285. [Google Scholar] [CrossRef] [Green Version]
  7. Yang, T.Y.; Lim, H.M.; Wei, B.Y.; Wu, C.Y.; Lin, C.K. UV enhancement of the gas sensing properties of nano-TiO2. Rev. Adv. Mater. Sci. 2003, 4, 48–54. [Google Scholar]
  8. Gong, J.; Li, Y.; Chai, X.; Hu, Z.; Deng, Y. UV-light-activated ZnO fibers for organic gas sensing at room temperature. J. Phys. Chem. C 2010, 114, 1293–1298. [Google Scholar] [CrossRef]
  9. Lu, G.; Xu, J.; Sun, J.; Yu, Y.; Zhang, Y.; Liu, F. UV-enhanced room temperature NO2 sensor using ZnO nanorods modified with SnO2 nanoparticles. Sens. Actuators B 2012, 162, 82–88. [Google Scholar] [CrossRef]
  10. Fabbri, B.; Gaiardo, A.; Giberti, A.; Guidi, V.; Malagù, C.; Martucci, A.; Sturaro, M.; Zonta, G.; Gherardi, S.; Bernardoni, P. Chemoresistive properties of photo-activated thin and thick ZnO films. Sens. Actuators B 2016, 222, 1251–1256. [Google Scholar] [CrossRef]
  11. Siwińska-Stefańska, K.; Kubiak, A.; Piasecki, A.; Goscianska, J.; Nowaczyk, G.; Jurga, S.; Jesionowski, T. TiO2-ZnO binary oxide systems: Comprehensive characterization and tests of photocatalytic activity. Materials 2018, 11, 841. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  12. Dulin, F.H.; Rase, D.E. Phase equilibria in the system ZnO-TiO2. J. Am. Ceram. Soc. 1960, 43, 125–131. [Google Scholar] [CrossRef]
  13. Bartram, S.F.; Slepetys, R.A. Compound formation and crystal structure in the system ZnO-TiO2. J. Am. Ceram. Soc. 1961, 44, 493–499. [Google Scholar] [CrossRef]
  14. Hosono, E.; Fujihara, S.; Onuki, M.; Kimura, T. Low-temperature synthesis of nanocrystalline zinc titanate materials with high specific surface area. J. Am. Ceram. Soc. 2004, 87, 1785–1788. [Google Scholar] [CrossRef]
  15. Mohammadi, M.R.; Fray, D.J. Low temperature nanostructured zinc titanate by an aqueous particulate sol-gel route: Optimization of heat treatment condition based on Zn:Ti molar ratio. J. Eur. Ceram. Soc. 2010, 30, 947–961. [Google Scholar] [CrossRef]
  16. Nicholas, T.N.; Michael, K.S.; Suresh, C.P. Crystallization and phase-transition characteristics of sol-gel-synthesized zinc titanates. Chem. Mater. 2011, 23, 1496–1504. [Google Scholar]
  17. Ray, S.; Das, P.; Banerjee, B.; Bhaumik, A.; Mukhopadhyay, C. Cubic perovskite ZnTiO3 nanopowder as a recyclable heterogeneous catalyst for the synthesis of 1,6-naphthyridines in water. ChemPlusChem 2015, 80, 731–739. [Google Scholar] [CrossRef]
  18. Chi, Y.; Yuan, Q.; Hou, S.; Zhao, Z. Synthesis and characterization of mesoporous ZnTiO3 rods via a polyvinylpyrrolidone assisted sol-gel method. Ceram. Int. 2016, 42, 5094–5099. [Google Scholar] [CrossRef]
  19. Pawar, R.C.; Kang, S.; Park, J.H.; Kim, J.H.; Ahn, S.; Lee, C.S. Evaluation of a multi-dimensional hybrid photocatalyst for enrichment of H2 evolution and elimination of dye/non-dye pollutants. Catal. Sci. Technol. 2017, 7, 2579–2590. [Google Scholar] [CrossRef]
  20. Wu, S.P.; Luo, J.H.; Cao, S.X. Microwave dielectric properties of B2O3-doped ZnTiO3 ceramics made with sol-gel technique. J. Alloys Compd. 2010, 502, 147–152. [Google Scholar] [CrossRef]
  21. Kong, J.Z.; Li, A.D.; Zhai, H.F.; Li, H.; Yan, Q.Y.; Ma, J.; Wu, D. Preparation, characterization and photocatalytic properties of ZnTiO3 powders. J. Hazard. Mater. 2009, 171, 918–923. [Google Scholar] [CrossRef] [PubMed]
  22. Yan, X.; Zhao, C.L.; Zhou, Y.L.; Wu, Z.J.; Yuan, J.M.; Li, W.S. Synthesis and characterization of ZnTiO3 with high photocatalytic activity. Trans. Nonferrous Met. Soc. China 2015, 25, 2272–2278. [Google Scholar] [CrossRef]
  23. Perween, S.; Ranjan, A. Improved visible-light photocatalytic activity in ZnTiO3 nanopowder prepared by sol-electrospinning. Sol. Energy Mater. Sol. Cells 2017, 163, 148–156. [Google Scholar] [CrossRef]
  24. Kubiak, A.; Siwińska-Ciesielczyk, K.; Bielan, Z.; Zielińska-Jurek, A.; Jesionowski, T. Synthesis of highly crystalline photocatalysts based on TiO2 and ZnO for the degradation of organic impurities under visible-light irradiation. Adsorption 2019, 25, 309–325. [Google Scholar] [CrossRef] [Green Version]
  25. Yadav, B.C.; Yadav, A.; Singh, S.; Singh, K. Nanocrystalline zinc titanate synthesized via physicochemical route and its application as liquefied petroleum gas sensor. Sens. Actuators B 2013, 177, 605–611. [Google Scholar] [CrossRef]
  26. Abdul Haroon Rashid, S.S.A.; Sabri, Y.M.; Kandjani, A.E.; Harrison, C.J.; Balasubramanyam, R.K.C.; Gaspera, E.D.; Field, M.R.; Bhargava, S.K.; Tricoli, A.; Wlodarski, W.; et al. Zinc titanate nanoarrays with superior optoelectrochemical properties for chemical sensing. ACS Appl. Mater. Interfaces 2019, 11, 29255–29267. [Google Scholar] [CrossRef]
  27. Liu, S.; Tang, Z.R.; Sun, Y.; Colmenares, J.C.; Xu, Y.J. One-dimension-based spatially ordered architectures for solar energy conversion. Chem. Soc. Rev. 2015, 44, 5053–5075. [Google Scholar] [CrossRef]
  28. Wang, X.; Feng, J.; Bai, Y.; Zhang, Q.; Yin, Y. Synthesis, properties, and applications of hollow micro-/nanostructures. Chem. Rev. 2016, 116, 10983–11060. [Google Scholar] [CrossRef]
  29. Yu, Y.H.; Xia, M. Preparation and characterization of ZnTiO3 powders by sol-gel process. Mater. Lett. 2012, 77, 10–12. [Google Scholar] [CrossRef]
  30. Liu, X. Molten salt synthesis of ZnTiO3 powders with around 100 nm grain size crystalline morphology. Mater. Lett. 2012, 80, 69–71. [Google Scholar] [CrossRef]
  31. Bobowska, I.; Opasinńska, A.; Wypych, A.; Wojciechowski, P. Synthesis and dielectric investigations of ZnTiO3 obtained by a soft chemistry route. Mater. Chem. Phys. 2012, 134, 87–92. [Google Scholar] [CrossRef]
  32. Lim, J.; Cui, H.; Mu, D.; Liu, Y.; Guan, T.; Xia, Z.; Jiang, L.; Zuo, J.; Tan, C.; You, H. Synthesis and characterization of rGO decorated cubic ZnTiO3 rods for solar light-induced photodegradation of rhodamine B. New J. Chem. 2019, 43, 3374–3382. [Google Scholar]
  33. Su, P.G.; Chen, F.Y.; Wei, C.H. Simple one-pot polyol synthesis of Pd nanoparticles, TiO2 microrods and reduced graphene oxide ternary composite for sensing NH3 gas at room temperature. Sens. Actuators B 2018, 254, 1125–1132. [Google Scholar] [CrossRef]
  34. Pan, G.H.; Hayakawa, T.; Nogami, M.; Hao, Z.; Zhang, X.; Qu, X.; Zhang, J. Zinc titanium glycolate acetate hydrate and its transformation to zinc titanate microrods: Synthesis, characterization and photocatalytic properties. RSC Adv. 2015, 5, 88590–88601. [Google Scholar] [CrossRef]
  35. Sharma, U.; Jeevanandam, P. Synthesis temperature dependent morphological evolution in zinc titanate heteronanostructures and their application in environmental remediation. ChemistrySelect 2016, 1, 6382–6395. [Google Scholar] [CrossRef]
  36. Jiang, X.; Wang, Y.; Herricks, T.; Xia, Y. Ethylene glycol-mediated synthesis of metal oxide nanowires. J. Mater. Chem. 2004, 14, 695–703. [Google Scholar] [CrossRef]
  37. You, L.; Wang, T.; Ge, J. When mesoporous silica meets the alkaline polyelectrolyte: A controllable synthesis of functional and hollow nanostructures with a porous shell. Chem. Eur. J. 2013, 19, 2142–2149. [Google Scholar] [CrossRef]
  38. Sun, H.; Wang, L.; Chu, D.; Ma, Z.; Wang, A. Facile fabrication of multishelled Cr2O3 hollow microspheres with enhanced gas sensitivity. Mater. Lett. 2015, 140, 158–161. [Google Scholar] [CrossRef]
  39. Reddy, K.H.; Martha, S.; Parida, K.M. Fabrication of novel p-BiOI/n-ZnTiO3 heterojunction for degradation of rhodamine 6G under visible light irradiation. Inorg. Chem. 2013, 52, 6390–6401. [Google Scholar] [CrossRef]
  40. Surendar, T.; Kumar, S.; Shanker, V. Influence of La-doping on phase transformation and photocatalytic properties of ZnTiO3 nanoparticles synthesized via modified sol-gel method. Phys. Chem. Chem. Phys. 2014, 16, 728–735. [Google Scholar] [CrossRef]
  41. Dhivya, P.; Prasad, A.K.; Sridharan, M. Nanostructured TiO2 films: Enhanced NH3 detection at room temperature. Ceram. Int. 2014, 40, 409–415. [Google Scholar] [CrossRef]
  42. Li, X.; Zhao, Y.; Wang, X.; Wang, J.; Gaskov, A.M.; Akbar, S.A. Reduced graphene oxide (rGO) decorated TiO2 microspheres for selective room-temperature gas sensors. Sens. Actuators B 2016, 230, 330–336. [Google Scholar] [CrossRef]
  43. Ye, Z.; Tai, H.; Xie, T.; Su, Y.; Yuan, Z.; Liu, C.; Jiang, Y. A facile method to develop novel TiO2/rGO layered film sensor for detecting ammonia at room temperature. Mater. Lett. 2016, 165, 127–130. [Google Scholar] [CrossRef]
  44. Wang, J.; Yang, P.; Wei, X. High-performance, room-temperature, and no-humidity impact ammonia sensor based on heterogeneous nickel oxide and zinc oxide nanocrystals. ACS Appl. Mater. Interfaces 2015, 7, 3816–3824. [Google Scholar] [CrossRef]
  45. Mhlongo, G.H.; Motaung, D.E.; Swart, H.C. Pd2+ doped ZnO nanostructures: Structural, luminescence and gas sensing properties. Mater. Lett. 2015, 160, 200–205. [Google Scholar] [CrossRef]
  46. Su, P.G.; Yang, L.Y. NH3 gas sensor based on Pd/SnO2/RGO ternary composite operated at room-temperature. Sens. Actuators B 2016, 223, 202–208. [Google Scholar] [CrossRef]
  47. Hieu, N.V.; Quang, V.V.; Hoa, N.D.; Kim, D. Preparing large-scale WO3 nanowire like structure for high sensitivity NH3 gas sensor through a simple route. Curr. Appl. Phys. 2011, 11, 657–661. [Google Scholar] [CrossRef]
  48. Shahabuddin, M.D.; Sharma, A.; Kumar, J.; Tomar, M.; Umar, A.; Gupta, V. Metal clusters activated SnO2 thin film for low level detection of NH3 gas. Sens. Actuators B 2014, 194, 410–418. [Google Scholar] [CrossRef]
  49. Yu, S.; Kan, K.; Yang, Y.; Jiang, C.; Gao, J.; Jing, L.; Shen, P.; Li, L.; Shi, K. Enhanced NH3 gas sensing performance based on electrospun alkaline-earth metals composited SnO2 nanofibers. J. Alloys Compd. 2015, 618, 240–247. [Google Scholar]
Sensors 20 00046 g001 550
Figure 1. (a) The structure of the NH3 gas sensor and (b) the measurement system for testing the gas sensors.
Figure 1. (a) The structure of the NH3 gas sensor and (b) the measurement system for testing the gas sensors.
Sensors 20 00046 g001
Sensors 20 00046 g002 550
Figure 2. The XRD patterns of the DSH ZnTiO3 microrods that were fabricated via the self-templating approach, followed (a) by calcining and (b) without calcining.
Figure 2. The XRD patterns of the DSH ZnTiO3 microrods that were fabricated via the self-templating approach, followed (a) by calcining and (b) without calcining.
Sensors 20 00046 g002
Sensors 20 00046 g003 550
Figure 3. The SEM images of the DSH ZnTiO3 microrods that were fabricated via the self-templating approach, followed by calcining: (a) low magnification and (b) high magnification.
Figure 3. The SEM images of the DSH ZnTiO3 microrods that were fabricated via the self-templating approach, followed by calcining: (a) low magnification and (b) high magnification.
Sensors 20 00046 g003
Sensors 20 00046 g004 550
Figure 4. The TEM images of the DSH ZnTiO3 microrod: (a) low-magnification TEM, (b) high-magnification TEM, (c) HRTEM (the inset is the corresponding SAED pattern), (d) EDX elemental maps and (e) EDX spectrum.
Figure 4. The TEM images of the DSH ZnTiO3 microrod: (a) low-magnification TEM, (b) high-magnification TEM, (c) HRTEM (the inset is the corresponding SAED pattern), (d) EDX elemental maps and (e) EDX spectrum.
Sensors 20 00046 g004
Sensors 20 00046 g005 550
Figure 5. Schematic illustration of the fabrication of DSH ZnTiO3 microrods by the self-templating approach.
Figure 5. Schematic illustration of the fabrication of DSH ZnTiO3 microrods by the self-templating approach.
Sensors 20 00046 g005
Sensors 20 00046 g006 550
Figure 6. The response (S) of intrinsic TiO2 microrods, ZnTiO3 powders, DSH ZnTiO3 microrods, and DSH ZnTiO3 microrods in the dark, in 100 ppm NH3 gas at room temperature.
Figure 6. The response (S) of intrinsic TiO2 microrods, ZnTiO3 powders, DSH ZnTiO3 microrods, and DSH ZnTiO3 microrods in the dark, in 100 ppm NH3 gas at room temperature.
Sensors 20 00046 g006
Sensors 20 00046 g007 550
Figure 7. (a) The response (S) of the DSH ZnTiO3 microrods to various concentration of NH3 gas at room temperature, and (b) the linear dependence of the response (S) of the DSH ZnTiO3 microrods on the concentration of NH3 gas at room temperature. The sensitivity ( Δ S Δ C ) is determined from the slope of the linear curve.
Figure 7. (a) The response (S) of the DSH ZnTiO3 microrods to various concentration of NH3 gas at room temperature, and (b) the linear dependence of the response (S) of the DSH ZnTiO3 microrods on the concentration of NH3 gas at room temperature. The sensitivity ( Δ S Δ C ) is determined from the slope of the linear curve.
Sensors 20 00046 g007
Sensors 20 00046 g008 550
Figure 8. The response and recovery of the DSH ZnTiO3 microrods to 5 ppm NH3 at room temperature.
Figure 8. The response and recovery of the DSH ZnTiO3 microrods to 5 ppm NH3 at room temperature.
Sensors 20 00046 g008
Sensors 20 00046 g009 550
Figure 9. The response and recover times vs. the NH3 gas concentration. (■) response time and (▲) recovery time.
Figure 9. The response and recover times vs. the NH3 gas concentration. (■) response time and (▲) recovery time.
Sensors 20 00046 g009
Sensors 20 00046 g010 550
Figure 10. The effect of the ambient humidity on the response (S) of the DSH ZnTiO3 microrods.
Figure 10. The effect of the ambient humidity on the response (S) of the DSH ZnTiO3 microrods.
Sensors 20 00046 g010
Sensors 20 00046 g011 550
Figure 11. The response (S) of the DSH ZnTiO3 microrods to various gases.
Figure 11. The response (S) of the DSH ZnTiO3 microrods to various gases.
Sensors 20 00046 g011
Sensors 20 00046 g012 550
Figure 12. The long-term stability of a NH3 gas sensor based on DSH ZnTiO3 microrods (dotted line as the average response (S) value). (■) 50 ppm and (▲) 5 ppm NH3 gas.
Figure 12. The long-term stability of a NH3 gas sensor based on DSH ZnTiO3 microrods (dotted line as the average response (S) value). (■) 50 ppm and (▲) 5 ppm NH3 gas.
Sensors 20 00046 g012
Sensors 20 00046 g013 550
Figure 13. The real-time resistance of DSH ZnTiO3 microrods as a function of time (s) toward different NH3 concentrations from 1 to 200 ppm.
Figure 13. The real-time resistance of DSH ZnTiO3 microrods as a function of time (s) toward different NH3 concentrations from 1 to 200 ppm.
Sensors 20 00046 g013
Table
Table 1. Comparison of the performance of the NH3 gas sensor developed herein with the literature.
Table 1. Comparison of the performance of the NH3 gas sensor developed herein with the literature.
Sensing MaterialOperating Temperature (°C)Detection Limit (ppm)Response/Recovery Time (s)References
TiO225534/90[41]
TiO2 microspheres/RGO255-/-[42]
TiO2/RGO25-55/-[43]
ZnO/NiO251520/90[44]
ZnO/Pd20030198/334[45]
Pd NPs/TiO2 MRs/RGO252.4420/3000[46]
DSH ZnTiO3 microrods25193/363This work

Share and Cite

MDPI and ACS Style

Su, P.-G.; Liu, X.-H. Preparation and NH3 Gas-Sensing Properties of Double-Shelled Hollow ZnTiO3 Microrods. Sensors 2020, 20, 46. https://doi.org/10.3390/s20010046

AMA Style

Su P-G, Liu X-H. Preparation and NH3 Gas-Sensing Properties of Double-Shelled Hollow ZnTiO3 Microrods. Sensors. 2020; 20(1):46. https://doi.org/10.3390/s20010046

Chicago/Turabian Style

Su, Pi-Guey, and Xiang-Hong Liu. 2020. "Preparation and NH3 Gas-Sensing Properties of Double-Shelled Hollow ZnTiO3 Microrods" Sensors 20, no. 1: 46. https://doi.org/10.3390/s20010046

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop