Tailoring the structure of metal oxide nanostructures towards enhanced sensing properties for environmental applications

The present article reviews recent works in our laboratory about the sensing properties to toxic gases using nanostructured WO(3), TiO(2), FTiO(2), and CuO functionalized quartz crystal microbalance (QCM) sensors. WO(3) and TiO(2) functionalized QCM sensors have much shorter response time than those functionalized by conventional hydrogen-bond acidic branched copolymers for detection of dimethyl methylphosphonate (DMMP). FTiO(2) functionalized QCM sensors can improve the gas sensing characteristics by shortening the response time but at the price of partial irreversibility. The sensing mechanism was examined by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Varied CuO nanostructures were synthesized by simple modulation of reaction conditions. All the as-prepared CuO was applied on QCM resonators and explored for HCN sensing. Surprisingly, responses of all the sensors to HCN were found to be in an opposite direction as compared with other common volatile substances, offering excellent selectivity for HCN detection. The sensitivity was very high, and the response and recovery were very fast. Comparison of the specific surface areas of CuO nanostructures showed that CuO of higher surface area is more sensitive than that of lower surface area, indicating that the specific surface area of these CuO nanostructures plays an important role in the sensitivity of related sensors. Based on experimental results, a sensing mechanism was proposed in which a surface redox reaction occurs between CuO and Cu(2)O on the CuO nanostructures reversibly upon contact with HCN and air, respectively. The CuO functionalized QCM sensors are considered to be a promising candidate for trace HCN gas detection in practical applications.     

Preparation of ZnO Nanowires and Study of Surface‐adsorbate Interaction by Fourier‐Transform Infrared Spectroscopy

To study the surface‐adsorbate properties of ZnO nanowires, a hydrothermal method was modified to grow ZnO nanowires directly on ZnSe, which were then characterized by attenuated total reflection infrared (ATR‐IR) spectroscopy. To prepare ZnO nanowires directly on ATR sensing element of ZnSe, ZnO seed layers were first formed by annealing of ZnO seeds on ZnSe surfaces. The ZnO seed layers then were exposed to growth solution, forming ZnO nanowires directly on the ATR crystals. The interaction properties of the resulting surfaces were studied by an ATR‐IR method. The diameter, length and distribution of the ZnO nanowires can be tuned by adjusting the growth conditions, particularly the growing time and the concentrations of reagents. Two surfaces, namely Zn‐rich and Zn‐O ion‐pair surfaces were studied in detail for their adsorption properties toward compounds bearing different functional groups. By examination of several volatile organic compounds (VOCs), it was found that the Zn‐rich surface is less selective and interacts with compounds bearing the functional groups of amino and hydroxyl. The Zn‐O ion‐pair surface is more selective and a much stronger interaction was observed with non‐aromatic amino compounds. These results indicate that the improving of the selectivity of a ZnO‐based sensing device can be achieved by tuning the surface structure of the ZnO nanomaterials.     

Growth and characterization of Cl-doped ZnO hexagonal nanodisks

Cl-doped ZnO nanodisks were grown on a Si(111) substrate using a thermal evaporation method. The prepared nanodisks exhibited a hexagonal shape with an average thickness of 50 nm and average diagonal of 270 nm. In addition, undoped ZnO disks with hexagonal shape were grown under the same conditions, but the sizes of these undoped ZnO disks were on the micrometer order. A possible mechanism was proposed for the growth of the Cl-doped ZnO nanodisks, and it was shown that the Cl¹⁻ anions play a crucial role in controlling the size. X-ray diffraction and Raman spectroscopy clearly showed an extension in the crystal lattice of ZnO because of the presence of chlorine. In addition, these nanodisks produced a strong photoluminescence emission peak in the ultraviolet (UV) region and a weak peak in the green region of the electromagnetic spectrum. Furthermore, the UV peak of the Cl-doped ZnO nanodisks was blueshifted with respect to that of the undoped ZnO disks.     

Carbon Quantum Dots Co‐catalyzed with ZnO Nanoflowers and Poly (CTAB) Nanosensor for Simultaneous Sensitive Detection of Paracetamol and Ciprofloxacin in Biological Samples

A novel platform based incorporation of carbon quantum dots (CQDs) and zinc oxide nanoflowers (ZnO‐NFs) decorated with poly cetyltrimethylammonium bromide (CTAB) was developed as electrochemical sensor for the sensitive and selective simultaneous detection of Paracetamol (PAR) and Ciprofloxacin (CIP) in biological samples. For this, CQDs and ZnO‐NFs were first deposited on a glassy carbon electrode (GCE) and subsequently a Poly (CTAB) layer was grown onto their surfaces through electro‐polymerization. The synthesized nanostructures and the corresponding fabricated sensor were characterized by the techniques of TEM, XRD, FE‐SEM, and EDX analysis. Moreover electrochemical characterization by CV and DPV were performed to elucidate the construction process and electron transfer abilities of the CQDs/ZnO‐NFs/Poly(CTAB)/GCE. Increased sensitivity and efficiency of this sensing system was obtained due to the synergistic effects of CQDs, ZnO‐NFs and Poly (CTAB) with multi‐signal amplification. Under the optimum conditions, the DPV response of proposed sensor to PAR and CIP was linear at 0.05–30.0 μM and 0.01–30.0 μM, with the detection limit of 2.47 nM and 1.97 nM respectively. The sensor possessed high stability, reproducibility, sensitivity, and selectivity toward PAR and CIP detection, over potential interferents and presented high recovery percentage in the real sample matrices.     

CuO–ZnO Micro/Nanoporous Array‐Film‐Based Chemosensors: New Sensing Properties to H2S

CuO–ZnO micro/nanoporous array‐films are synthesized by transferring a solution‐dipped self‐organized colloidal template onto a device substrate and sequent heat treatment. Their morphologies and structures are characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy, and X‐ray photoelectron spectrum analysis. Based on the sensing measurement, it is found that the CuO–ZnO films prepared with the composition of [Cu²⁺]/[Zn²⁺]=0.005, 0.01, and 0.05 all show a nice sensitivity to 10 ppm H₂S. Interestingly, three different zones exist in the patterns of gas responses versus H₂S concentrations: a platform zone, a rapidly increasing zone, and a slowly increasing zone. Further experiments show that the hybrid CuO–ZnO porous film sensor exhibits shorter recovery time and better selectivity to H₂S gas against other interfering gases at a concentration of 10 ppm. These new sensing properties may be due to a depletion layer induced by p–n junction between p‐type CuO and n‐type ZnO and high chemical activity of CuO to H₂S. This work will provide a new construction route of ZnO‐based sensing materials, which can be used as H₂S sensors with high performances.     

Towards high‐performance biopackaging: barrier and mechanical properties of dual‐action polycaprolactone/zinc oxide nanocomposites

The properties of nanocomposites of biodegradable polycaprolactone containing zinc oxide (ZnO) nanoparticles with diverse morphologies, that is, ZnO nanospheres, nanorods, and nanodisks are investigated. It is demonstrated for the first time that the dual action of the ZnO nanoparticles reduces the gas permeability of the nanocomposites via two mechanisms: first by the creation of a tortuous path and second by gas adsorption. Depending on the morphology of the particles, the oxygen permeability can be reduced by more than 60%. Tensile tests show that the nanocomposites remain very ductile. The nominal strain for all nanocomposites is higher than 500% before fracture occurs. The Young's modulus and tensile strength of the nanocomposites increase at higher ZnO concentrations. This behavior is more pronounced in the case of ZnO nanorods. As a result, the incorporation of ZnO nanoparticles into (bio)polymers provides an opportunity to manufacture polymer‐based nanocomposite materials, resulting in the production of high‐performance (bio)packaging. Copyright © 2011 John Wiley & Sons, Ltd.     

Property–Performance Control of Multidimensional,Hierarchical, Single‐Crystalline ZnO Nanoarchitectures

Diverse morphologies of multidimensional hierarchical single‐crystalline ZnO nanoarchitectures including nanoflowers, nanobelts, and nanowires are obtained by use of a simple thermal evaporation and vapour‐phase transport deposition technique by placing Au‐coated silicon substrates in different positions inside a furnace at process temperatures as low as 550 °C. The nucleation and growth of ZnO nanostructures are governed by the vapour–solid mechanism, as opposed to the commonly reported vapour–liquid–solid mechanism, when gold is used in the process. The morphological, structural, compositional and optical properties of the synthesized ZnO nanostructures can be effectively tailored by means of the experimental parameters, and these properties are closely related to the local growth temperature and gas‐phase supersaturation at the sample position. In particular, room‐temperature photoluminescence measurements reveal an intense near‐band‐edge ultraviolet emission at about 386 nm for nanobelts and nanoflowers, which suggests that these nanostructures are of sufficient quality for applications in, for example, optoelectronic devices.     

Surface Modifications and Optoelectronic Characterization of TiO2‐Nanoparticles: Design of New Photo‐Electronic Materials

TiO₂ nanoparticles are of great current interest for applications in photo‐electronic materials including light‐energy conversion, artificial photosynthetic systems as well as photocatalysis. The success of these applications relies on the exciton recombination dynamics and visible‐light sensitivity of the TiO₂ nanomaterials. Thus, in order to develop the highly efficient photo‐electronic materials absorbing visible light, different low dimensional TiO₂ nanostructures such as nanodiscs, nanofibers and nanochains were synthesized, and thereafter their surfaces were modified by incorporating with Sn‐porphyrins and heteropoly acid. The optoelectronic properties of the surface‐modified nanomaterials were investigated with regard to the optical properties and the surface exciton dynamics by using both steady‐state and ultrafast time‐resolved laser spectroscopic techniques including single nanoparticle photoluminescence technique. These results were correlated with the photo‐electronic properties including photocatalytic activities and solar cell efficiencies, indicating that the electron transfer mechanism in the modified nanostructures may be similar to the “Z‐scheme” of the plant photosynthetic system so that both photocatalytic activity and solar cell efficiencies were synergistically enhanced by using two color illumination.     

Local‐Curvature‐Controlled Non‐Epitaxial Growth of Hierarchical Nanostructures

Site‐selective growth on non‐spherical seeds provides an indispensable route to hierarchical complex nanostructures that are interesting for diverse applications. However, this has only been achieved through epitaxial growth, which is restricted to crystalline materials with similar crystal structures and physicochemical properties. A non‐epitaxial growth strategy is reported for hierarchical nanostructures, where site‐selective growth is controlled by the curvature of non‐spherical seeds. This strategy is effective for site‐selective growth of silica nanorods from non‐spherical seeds of different shapes and materials, such as α‐Fe₂O₃, NaYF₄, and ZnO. This growth strategy is not limited by the stringent requirements of epitaxy and is thus a versatile general method suitable for the preparation of hierarchical nanostructures with controlled morphologies and compositions to open up a verity of applications in self‐assembly, nanorobotics, catalysis, electronics, and biotechnology.     

Length‐Dependent Charge Generation from Vertical Arrays of High‐Aspect‐Ratio ZnO Nanowires

Aqueous chemical growth of zinc oxide nanowires is a flexible and effective approach to obtain dense arrays of vertically oriented nanostructures with high aspect ratio. Herein we present a systematic study of the different synthesis parameters that influence the ZnO seed layer and thus the resulting morphological features of the free‐standing vertically oriented ZnO nanowires. We obtained a homogeneous coverage of transparent conductive substrates with high‐aspect‐ratio nanowire arrays (length/diameter ratio of up to 52). Such nanostructured vertical arrays were examined to assess their electric and piezoelectric properties, and showed an electric charge generation upon mechanical compressive stress. The principle of energy harvesting with these nanostructured ZnO arrays was demonstrated by connecting them to an electronic charge amplifier and storing the generated charge in a series of capacitors. We found that the generated charge and the electrical behavior of the ZnO nanowires are strictly dependent on the nanowire length. We have shown the importance of controlling the morphological properties of such ZnO nanostructures for optimizing a nanogenerator device.     

Fabrication of Gold‐Directed Conducting Polymer Nanoarrays for High‐Performance Gas Sensor

Gold‐directed polypyrrole (PPy) nanoarrays are fabricated by hydrogel‐assisted nanotransfer edge printing (HnTEP) and electrochemical polymerization. Gold nanoarrays are fabricated through the HnTEP method, which involves metal deposition, hydrogel etching, and nanotransfer edge printing. By utilizing the well‐positioned gold nanostructures, PPy nanoarrays with smooth morphology and controllable dimensions are fabricated through in situ electrochemical polymerization, the results of which are characterized by scanning electron microscopy and atomic force microscopy. A gas sensor based on PPy nanoarrays results in excellent sensing capabilities towards NH₃ detection, especially the sensitivity and fast response. This method appears to be general and may aid in the future design and implementation of other active materials which can also be manipulated by the same procedure and serve as functional components for chemical sensing, optoelectronics, biodetection, and other applications.     

Hierarchically Self‐Assembled Star‐Shaped ZnO Microparticles for Electrochemical Sensing of Amines

Novel, hierarchically nanostructured, star‐shaped ZnO (SSZ) microparticles are synthesized by a hydrothermal synthetic route. The SSZ microparticles serve as effective platforms for electrochemical detection of amines in solution. The morphology and structure of the materials are characterized by X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and UV/Vis spectroscopy. The as‐synthesized SSZ microparticles comprise self‐assembled hexagonal prisms that possess nanometer and micrometer pores in their structure and on their surfaces—structural features that are conducive to sensing applications. An electrode fabricated by using the hierarchically nanostructured SSZ materials serve as a sensitive electrochemical sensor for detection of low concentrations of ethylenediamine, with a sensitivity of 2.98×10^?2 mA cm^?2 mm ^?1, a detection limit of 2.36×10^?2 mm , and a short response time of 8 s.     

Controlled growth of two-dimensional and one-dimensional ZnO nanostructures on indium tin oxide coated glass by direct electrodeposition

A simple electrochemical deposition technique is used to deposit ZnO nanostructures with diverse morphology directly on ITO-coated glass substrates at 70 degrees C. The concentration of the Zn(NO 3) 2.6H 2O electrolyte is important to controlling the dimensionality of the nanostructures, with formation of one-dimensional (1D) nanospikes and nanopillars (with 50-500 nm diameter) below 0.01 M and of two-dimensional (2D) nanowalls and nanodisks (with 50-100 nm wall/disk thickness) above 0.05 M. Glancing-incidence X-ray diffraction study shows their wurtzite structure and confirms the change in the preferred crystal plane orientation with the dimensionality of ZnO nanostructures. UV-vis spectroscopy reveals a higher transmittance from 2D nanostructures than from 1D nanostructures and their optical direct band gaps estimated to be 3.12-3.27 eV. Depth-profiling X-ray photoemission studies show the presence of Zn(OH) 2 outer layers on the ZnO nanostructures, with a higher Zn(OH) 2 moiety for 2D nanostructures relative to 1D nanostructures. Furthermore, a substantial quantity of Cl (provided by the KCl supporting electrolyte) is detected throughout the 2D nanostructures only. The photoemission data therefore affirm our proposed growth mechanism that involves capping of the preferred [0001] growth direction by Cl (-) ions under fast hydroxylation kinetics condition as observed at a higher Zn(NO 3) 2.6H 2O electrolyte concentration.     

Physicochemical Interaction of ZnO Fine Particles with 5‐Mono‐(4‐carboxyphenyl)‐10,15,20‐Triphenylporphyrin

This study deals with an investigation on the preparation and physicochemical interactions of ZnO nanoparticles with acid functionalized porphyrin [5‐mono‐(4‐carboxyphenyl)‐10,15,20‐triphenylporphyrin (CPTPP)] for photovoltaic applications in a detailed manner. Zinc acetate and sodium hydroxide were used as the starting materials for the synthesis of ZnO nanoparticles at 60 °C in an alcoholic medium. The freshly prepared fine particles were then functionalized with CPTPP. Both the virgin and pregnant ZnO particles were characterized by using UV‐Visible spectrophotometry (UV), fluorescence emission (PL), Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The band gap energy obtained for ZnO particles, having a value of 3.47 eV, shows significant quantum confinement effect and enhanced photophysical activity. FTIR analysis of the doped ZnO nanostructures showed the presences of some chemical species. SEM analysis revealed a clear change in the surface morphologies of undoped ZnO. The average crystallite size of nanoparticles, calculated from XRD peaks, was found in the nano regime. The lattice parameters calculated for ZnO nanocrystals were also found in good agreement with those given in the literature. From the enhancement in the red shift of the UV‐Vis spectra, it is concluded that hybridization of acid functionalized porphyrin can cause a significant expansion in the total absorption region of ZnO semiconductor for photovoltaic applications.     

Preparation of ZnO nanoparticle‐reinforced polyamide 6 composite by in situ‐coproduced method and their properties

Polyamide 6/ZnO nanocomposites (noted as PA6/ZnO) were prepared by an in situ co‐producing method, during which Zn₂(OH)₂CO₃ decomposed into nano‐ZnO in the process of the opening‐ring polymerization of caprolactam at high temperature. Transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, and differential scanning calorimetry were used to analyze the size and dispersive properties of nano‐ZnO, the crystallization and melting properties, the thermal properties, and crystal structure of PA6/ZnO composite, respectively. The results showed that the nano‐ZnO derived from Zn₂(OH)₂CO₃ via in situ polymerization of PA6‐ZnO was uniformly dispersed in PA6 matrix. However, the overall nano‐ZnO crystallization rate and crystal size in the PA6 matrix were hindered by the bulky PA6 molecular chains. The mechanical properties were evaluated using universal tensile and impact testing instruments. The results revealed that PA6/ZnO composite with 0.2% nano‐ZnO content possessed excellent tensile strength, enhanced by 75% in comparison with the pure PA6. The nano‐ZnO had little influence on the impact strength of PA6. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 165–170     

Controlled Orientation in a Bio‐Inspired Assembly of Ag/AgCl/ZnO Nanostructures Enables Enhancement in Visible‐Light‐Induced Photocatalytic Performance

In a bio‐inspired approach, polyamine‐mediated mineralization of ZnO was explored to develop an environmentally benign methodology for synthesizing Ag/AgCl/ZnO nanostructures. The assembling properties displayed by the polyamines to create composite structures was utilized to have the nanocomponents effectively interact with each other in a way that is desirable for the application envisaged. The polyamines, which act as a mineralizing agent for ZnO nanoparticles, also facilitate the formation of Ag/AgCl within ZnO under ambient conditions. Thus synthesized Ag/AgCl/ZnO nanostructures represent a multi‐heterojunction system in which the nanocomponents lead in a synergistic way to enhancement in the photocatalytic activity under visible‐light irradiation.     

Hierarchical Nitrogen‐Doped Flowerlike ZnO Nanostructure and Its Multifunctional Environmental Applications

Hierarchical nitrogen‐doped ZnO flowerlike nanostructures were synthesized on a large scale. These nanostructures were characterized by FESEM, HRTEM, XRD, FTIR, XPS, and TGA, and their suitability for multifunctional environmental applications was investigated. The experimental results demonstrated that the hierarchical N‐doped ZnO flowerlike nanostructure enhances the photodegradation of methyl blue (MB) and acid orange 7 (AO7) by presenting a large specific surface area and high light utilization rate, inhibits the growth of bacteria without light irradiation, and increases the permeate flux when used in a membrane filtration system. These advantages of the hierarchical N‐doped ZnO flowerlike nanostructure brings benefits to the environmental application fields.     

Potential of Gelatin‐Zinc Oxide Nanocomposite as Ascorbic Acid Sensor

We report on the studies relating to fabrication of gelatin B (GB) and zinc oxide (ZnO) based nanocomposite (GB‐ZnO) film deposited on indium‐tin‐oxide (ITO) glass plate, and used for the immobilization of ascorbate oxidase (AsOx) which was further used for ascorbic acid (AA) detection. The structural and morphological studies of GB‐ZnO, and AsOx/GB‐ZnO/ITO bioelectrodes were carried out using XRD, SEM and FTIR techniques. This bioelectrode showed a broad range of linearity (5–500 mg/dL), low detection limit (1 mg/dL), higher sensitivity (0.106 µA mg/dLcm^?2) and low value of the apparent Michaelis? Menten constant (K_m^app=0.35 mg/dL) for AA. Efforts are being made to utilize this electrode for sensing AA in real samples in a bid to develop a strip based sensor.     

Enhanced Thermocatalytic Activity of Porous Yellow ZnO Nanoflakes: Defect‐ and Morphology‐Induced Perspectives

Herein, we report a simple and effective strategy for the synthesis of yellow ZnO (Y‐ZnO) nanostructures with abundant oxygen vacancies on a large scale, through the sulfidation of ZnO followed by calcination. The developed strategy allows retention of the overall morphology of Y‐ZnO compared with pristine ZnO and the extent of oxygen vacancies can be tuned. The influence of oxygen deficiencies, the extent of defect sites, and the morphology of ZnO on its solution‐phase thermocatalytic activity has been evaluated in the synthesis of 5‐substituted‐1H‐tetrazoles with different nitriles and sodium azide. A reasonable enhancement in the reaction rate was achieved by using Y‐ZnO nanoflakes (Y‐ZnO NFs) as a catalyst in place of pristine ZnO NFs. The reaction was complete within 6 h at 110 °C with Y‐ZnO NFs, whereas it took 14 h at 120 °C with pristine ZnO NFs. The catalyst is easy to recycle without a significant loss in catalytic activity.     

Growth of Shape‐ and Size‐Selective Zinc Oxide Nanorods by a Microwave‐Assisted Chemical Bath Deposition Method: Effect on Photocatalysis Properties

Herein, we demonstrate the shape‐ and size‐selective growth of ZnO nanostructures on indium tin oxide‐coated glass substrates by using a microwave‐assisted chemical bath deposition method. By systematically controlling the deposition parameters, it is possible to produce shape‐ and size‐selective nanostructures with high alignment and uniformity. Specifically, the pH of the bath can be used to control the shape of rods from bundled structures to tapered and flat tips. Furthermore, the deposition temperature can be used to control the size of the ZnO array from 770 to 125 nm. The prepared rods were active catalysts in the degradation of methylene blue under UV radiation, and exhibited size‐dependent activity.