Lingtao Kong

Metal Oxide Nanostructures and Their Gas Sensing Properties: A Review

Metal oxide gas sensors are predominant solid-state gas detecting devices for domestic, commercial and industrial applications, which have many advantages such as low cost, easy production, and compact size. However, the performance of such sensors is significantly influenced by the morphology and structure of sensing materials, resulting in a great obstacle for gas sensors based on bulk materials or dense films to achieve highly-sensitive properties. Lots of metal oxide nanostructures have been developed to improve the gas sensing properties such as sensitivity, selectivity, response speed, and so on. Here, we provide a brief overview of metal oxide nanostructures and their gas sensing properties from the aspects of particle size, morphology and doping. When the particle size of metal oxide is close to or less than double thickness of the space-charge layer, the sensitivity of the sensor will increase remarkably, which would be called “small size effect”, yet small size of metal oxide nanoparticles will be compactly sintered together during the film coating process which is disadvantage for gas diffusion in them. In view of those reasons, nanostructures with many kinds of shapes such as porous nanotubes, porous nanospheres and so on have been investigated, that not only possessed large surface area and relatively mass reactive sites, but also formed relatively loose film structures which is an advantage for gas diffusion. Besides, doping is also an effective method to decrease particle size and improve gas sensing properties. Therefore, the gas sensing properties of metal oxide nanostructures assembled by nanoparticles are reviewed in this article. The effect of doping is also summarized and finally the perspectives of metal oxide gas sensor are given.

Removal of cobalt ions from aqueous solution by an amination graphene oxide nanocomposite

A newly designed amination graphene oxide (GO-NH2), a superior adsorption capability to that of activated carbon, was fabricated by graphene oxide (GO) combining with aromatic diazonium salt. The resultant GO-NH2 maintained a high surface area of 320 m(2)/g. When used as an adsorbent, the GO-NH2 demonstrated a very quick adsorption property for the removal of Co(II) ions, more than 90% of Co(II) ions could be removed within 5 min for dilute solutions at 0.3g/L adsorbent dose. The adsorption capability approaches 116.35 mg/g, which is one of the highest capabilities of todays materials. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that the Co(II) ions adsorption on GO-NH2 was a spontaneous process. Considering the superior adsorption capability, the GO-NH2 filter membrane was fabricated for the removal of Co(II) ions. Membrane filtration experiments revealed that the removal capabilities of the materials for cobalt ions depended on the membranes thickness, flow rate and initial concentration of Co(II) ions. The highest percentage removal of Co(II) exceeds 98%, indicating that the GO-NH2 is one of the very suitable membrane materials in environmental pollution management.

Highly Sensitive SERS Detection of Hg2+ Ions in Aqueous Media Using Gold Nanoparticles/Graphene Heterojunctions

Gold nanoparticles (AuNPs)/reduced graphene oxide (rGO) heterojunctions were synthesized directly on SiO2/Si substrates via a seed-assisted growth process. The in situ chemical fabrication strategy has been proven to be quite simple and efficient for generating highly active surface-enhanced Raman scattering (SERS) substrates due to synergistic enhanced protocol from rGO and AuNPs. The SERS substrates with AuNPs/rGO heterojunctions have been utilized for trace analysis of mercury(II) ions via thymine-Hg(2+)-thymine coordination. Thereby, very low limits of detection, i.e., 0.1 nM or 20 ppt for Hg(2+), can be achieved in contrast with some other SERS subsrtates, which suggests that the heterojunctions are appropriate as versatile surface-enhanced substrates applied in chemical sensing or biosensing.

Stripping voltammetric detection of mercury(II) based on a surface ion imprinting strategy in electropolymerized microporous poly(2-mercaptobenzothiazole) films modified glassy carbon electrode

This work reports a surface ion imprinting strategy in electropolymerized microporous poly(2-mercaptobenzothiazole) (MPMBT) films at the surface of glassy carbon electrode (GCE) for the electrochemical detection of Hg(II). The Hg(II)-imprinted MPMBT/GCE exhibits larger binding to functionalized capacity, faster binding kinetics and higher selectivity to template Hg(II) due to their high ratio of surface-imprinted sites, larger surface-to-volume ratios, the complete removal of Hg(II) templates and larger affinity to Hg(II). The square wave anodic stripping voltammetry (SW ASV) response of the Hg(II)-imprinted MPMBT/GCE to Hg(II) is ca. 3.0 and 5.9 times larger than that at the direct imprinted poly(2-mercaptobenzothiazole) modified GCE and non-imprinted MPMBT/GCE sensor, respectively; and the detection limit for Hg(II) is 0.1nM (which is well below the guideline value given by the World Health Organization). Excellent wide linear range (1.0-160.0nM) and good repeatability (relative standard deviation of 2.5%) were obtained for Hg(II). The interference experiments showed that mercury signal was not interfered in the presence of Pb(II), Cd(II), Zn(II), Cu(II) and Ag(I), respectively. These values, particularly the high sensitivity and excellent selectivity compared favorably with previously reported methods in the area of electrochemical Hg(II) detection, demonstrate the feasibility of using the prepared Hg(II)-imprinted MPMBT/GCE for efficient determination of Hg(II) in aqueous environmental samples.

Parts per billion-level detection of benzene using SnO2/graphene nanocomposite composed of sub-6 nm SnO2 nanoparticles

In the present work, the SnO(2)/graphene nanocomposite composed of 4-5 nm SnO(2) nanoparticles was synthesized using a simple wet chemical method for ppb-level detection of benzene. The formation mechanism of the nanocomposite was investigated systematically by means of simultaneous thermogravimetry analysis, X-ray diffraction, and X-ray photoelectron spectroscopy cooperated with transmission electron microscopy observations. The SnO(2)/graphene nanocomposite showed a very attractive improved sensitivity to toxic volatile organic compounds, especially to benzene, compared to a traditional SnO(2). The responses of the nanocomposite to benzene were a little higher than those to ethanol and the detection limit reached 5 ppb to benzene which is, to our best knowledge, far lower than those reported previously.

Synthesis of novel decorated one-dimensional gold nanoparticle and its application in ultrasensitive detection of insecticide

Contamination of soil, groundwater and food with methyl parathion, which is one of the most hazardous insecticides, is causing wide concern. Motivated by the urgent demand for trace analysis of insecticide from environmental samples, searching for a novel highly sensitive or selective analytical approach has been a longstanding interest. The as-prepared one dimensional gold nanoparticles, with different aspect ratios, have been decorated with mono-6-thio-β-cyclodextrin so as to efficiently capture and detect methyl parathion insecticide via a surface enhanced Raman scattering (SERS) technique for the first time. A detailed comparison among different aspect ratios of the one dimensional gold nanoparticles suggests that the one dimensional gold nanoparticles with aspect ratio 2 can be provided as an excellent SERS active substrate for detecting the insecticide in the present study. Due to the efficient formation of a host–guest complex between the hybridized cavity and methyl parathion, identification of the insecticide can be observed at picomolar level according to the fingerprint Raman peaks. Excellent sensitivity and selectivity for detection of the insecticide using the hybridized one dimensional gold nanoparticles without a Raman label indicate that it is a simple and ultrasensitive approach for detecting insecticides in contrast with some other traditional detection approaches.

Single-Walled Carbon Nanotube/Pyrenecyclodextrin Nanohybrids for Ultrahighly Sensitive and Selective Detection of p-Nitrophenol

Electrochemical detection of p-nitrophenol (P-NP) using a highly sensitive and selective platform based on single-walled carbon nanotube/pyrenecyclodextrin (SWCNT/PyCD) nanohybrids is described for the first time. The electrochemical performance of the SWCNT/PyCD nanohybrid electrode was fully compared with bare glassy carbon, single-SWCNT, single-PyCD, and SWCNT/CD (without pyrene rings) electrodes. Besides the techniques of cyclic voltammetry and chronoamperometric transients, differential pulse voltammetry (DPV) has been used for the detection of P-NP without any interference from o-nitrophenol (O-NP) at the potentials of -0.80 and -0.67 V, respectively. The SWCNT/PyCD nanohybrid electrode is highly sensitive, and it shows an ultrahigh sensitivity of 18.7 μA/μM toward P-NP in contrast to the values reported previously. The detection limit (S/N = 3) of the SWCNT/PyCD nanohybrid electrode toward P-NP is 0.00086 μM (0.12 ppb), which is well below the allowed limit in drinking water, 0.43 μM, given by the U.S. Environmental Protection Agency (EPA). The analytical performance of the SWCNT/PyCD nanohybrid electrode toward P-NP is superior to the existing electrodes.

Performance of novel hydroxyapatite nanowires in treatment of fluoride contaminated water

Novel ultralong hydroxyapatite (HAP) nanowires were successfully prepared for fluoride removal for the first time. The fluoride adsorption on the HAP nanowires was studied on a batch mode. The results revealed that the adsorption data could be well described by the Freundlich model, and the adsorption kinetic followed the pseudo-second-order model. The maximum of adsorption capacity was 40.65 mg/g at pH 7.0 when the fluoride concentration is 200mg/L. The thermodynamic parameters suggested that the adsorption of fluoride was a spontaneous endothermic process. The FT-IR, XPS and Zeta potential analysis revealed that both anion exchange and electrostatic interactions were involved in the adsorption of fluoride. Furthermore, the HAP nanowires were made into HAP membrane through a simple process of suction filtration. Membrane filtration experiments revealed that the fluoride removal capabilities depended on the membrane thickness, flow rate and initial concentration of fluoride. The as-prepared membrane could remove fluoride efficiently through continues filtration. The filtered water amount could reach 350, 192, and 64 L/m(2) when the fluoride concentrations were 4, 5 and 8 ppm, respectively, using the HAP membrane with only 150 μm thickness. The as-synthesized ultralong HAP nanowires were thus demonstrated to be very effective and biocompatible adsorbents for fluoride removal from contaminated water.

Polystyrene/Ag nanoparticles as dynamic surface-enhanced Raman spectroscopy substrates for sensitive detection of organophosphorus pesticides

We report the use of Polystyrene/Ag (PS/Ag) nanoparticles as dynamic surface-enhanced Raman spectroscopy (dynamic-SERS) substrates for sensitive detection of low levels of organophosphorus pesticides. The PS particles clearly observed using Raman microscopy provide the masterplate for in situ growth of Ag NPs, leading to multiple active sites for SERS measurements. Besides obtaining the fingerprints of target molecules and recording time-resolved Raman spectra, this dynamic-SERS method can be used as an ultra-sensitive analytical technique which can enhance 1-2 orders of magnitude the signals of analytes in comparison to that of the traditional methods. On the other hand, importantly, it shows much better correlations between concentration and intensity than does the conventional SERS technique so that it can build the foundation for quantitative analysis of analytes. The as-prepared individual PS/Ag nanoparticle has been demonstrated for the sensitive detection of organophosphorus paraoxon and sumithion. SERS spectra are acquired at different concentrations of each pesticide and linear calibration curves are obtained by monitoring the strongest intensity value of bands arising from stronger stretching mode as a function of analyte concentration. The limits of detection and limits of quantitation are reported for two pesticides. The limit of detection for paraoxon is 96 nM (0.026 ppm) and for sumithion is 34 nM (0.011 ppm). The limits of quantitation are 152 nM (0.042 ppm) and 57 nM (0.016 ppm) for paraoxon and sumithion, respectively. It can be seen that these two organophosphorus pesticides can be detected in the low nM range based on this dynamic-SERS analytical method. Also, in the real sample experiments of paraoxon and sumithion, the results confirm that this dynamic-SERS technique would have potential applicability for quantitative analysis with slight interference.

Wide pH range for fluoride removal from water by MHS-MgO/MgCO3 adsorbent: Kinetic, thermodynamic and mechanism studies

A novel environment friendly adsorbent, micro-nano hierarchical structured flower-like MgO/MgCO3 (MHS-MgO/MgCO3), was developed for fluoride removal from water. The adsorbent was characterized and its defluoridation properties were investigated. Adsorption kinetics fitted well the pseudo-second-order model. Kinetic data revealed that the fluoride adsorption was rapid, more than 83-90% of fluoride could be removed within 30 min, and the adsorption equilibrium was achieved in the following 4 h. The fluoride adsorption isotherm was well described by Freundlich model. The maximum adsorption capacity was about 300 mg/g at pH=7. Moreover, this adsorbent possessed a very wide available pH range of 5-11, and the fluoride removal efficiencies even reached up to 86.2%, 83.2% and 76.5% at pH=11 for initial fluoride concentrations of 10, 20 and 30 mg/L, respectively. The effects of co-existing anions indicated that the anions had less effect on adsorption of fluoride except phosphate. In addition, the adsorption mechanism analysis revealed that the wide available pH range toward fluoride was mainly resulted from the exchange of the carbonate and hydroxyl groups on the surface of the MHS-MgO/MgCO3 with fluoride anions.