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Oxygen evolution reaction driven by NiO microflowers.

In this work we describe the Square Wave Anodic Stripping Voltammetry (SWASV) electrochemical technique for the determination of lead (Pb2+) and cadmium (Cd2+) metal ions at concentration of sub-part per billion (ppb) in aqueous solution. Moreover, simple and low-cost procedures for the fabrication of high performance working nano-electrode are reported. The electrode structure consists of a graphene paper (GP) $240~\mu \text{m}$ thick with the function of electrical conductor and substrate, a layer of nafion 0.5- $0.7~\mu \text{m}$ thick onto the graphene paper and bismuth nanoparticles embedded in the nafion thin layer. The bismuth nanoparticles were fabricated by electrodeposition starting from Bi(III) ions, employing a key step of hydrogen ions of nafion $\text{H}^{\mathbf {+}}$ exchange with bismuth ions Bi(III). This procedure is aimed to improve the bismuth nanoparticles concentration. The SWASV applied to the low-cost nanoelectrode allows detecting Pb2+ and Cd2+ at concentration as low as 0.1 ppb.

The low efficiency of water electrolysis mostly arises from the thermodynamic uphill oxygen evolution reaction. The efficiency can be greatly improved by rationally designing low-cost and efficient oxygen evolution anode materials. Herein, we report the synthesis of Ni–P alloys adopting a facile electroless plating method under mild conditions on nickel substrates. The relationship between the Ni–P properties and catalytic activity allowed us to define the best conditions for the electroless synthesis of highperformance Ni–P catalysts. Indeed, the electrochemical investigations indicated an increased catalytic response by reducing the thickness and Ni/P ratio in the alloy. Furthermore, the Ni–P catalysts with optimized size and composition deposited on Ni foam exposed more active sites for the oxygen evolution reaction, yielding a current density of 10 mA cm−2 at an overpotential as low as 335 mV, exhibiting charge transfer resistances of only a few ohms and a remarkable turnover frequency (TOF) value of 0.62 s−1 at 350 mV. The present study provides an advancement in the control of the electroless synthetic approach for the design and large-scale application of high-performance metal phosphide catalysts for electrochemical water splitting.

Surface decoration by means of metal nanostructures is an effective way to locally modify the electronic properties of materials. The decoration of ZnO nanorods by means of Au nanoparticles was experimentally investigated and modelled in terms of energy band bending. ZnO nanorods were synthesized by chemical bath deposition. Decoration with Au nanoparticles was achieved by immersion in a colloidal solution obtained through the modified Turkevich method. The surface of ZnO nanorods was quantitatively investigated by Scanning Electron Microscopy, Transmission Electron Microscopy and Rutherford Backscattering Spectrometry. The Photoluminescence and Cathodoluminescence of bare and decorated ZnO nanorods were investigated, as well as the band bending through Mott–Schottky electrochemical analyses. Decoration with Au nanoparticles induced a 10 times reduction in free electrons below the surface of ZnO, together with a decrease in UV luminescence and an increase in visible-UV intensity ratio. The effect of decoration was modelled with a nano-Schottky junction at ZnO surface below the Au nanoparticle with a Multiphysics approach. An extensive electric field with a specific halo effect formed beneath the metal–semiconductor interface. ZnO nanorod decoration with Au nanoparticles was shown to be a versatile method to tailor the electronic properties at the semiconductor surface.

A novel metal organic framework (MOF)-based composite was synthesized on a Cu substrate via a two-step route. An amorphous iron oxide/hydroxide layer was first deposited on a Cu foil through a sol–...

Nanostructured electrodes detecting bacteria or viruses through DNA hybridization represent a promising method, which may be useful in on-field applications where PCR-based methods are very expensive, time-consuming, and require trained personnel. Indeed, electrochemical sensors combine disposability, fast response, high sensitivity, and portability. Here, a low-cost and high-surface-area electrode, based on Au-decorated NiO nanowalls, demonstrates a highly sensitive PCR-free detection of a real sample of

The decoration of semiconductor nanostructures with small metallic clusters usually leads to an improvement of their properties in sensing or catalysis. Bimetallic cluster decoration typically is claimed to be even more effective. Here, we report a detailed investigation of the effects of Au, Pt or AuPt nanocluster decoration of ZnO nanorods on charge transport, photoluminescence and UV sensitivity. ZnO nanorods were synthesized by chemical bath deposition while decoration with small nanoclusters (2-3 nm in size) was achieved by a laser-ablation based cluster beam deposition technology. The structural properties were investigated by scanning electron microscopy, high resolution transmission electron microscopy, X-ray photoelectron spectroscopy and Rutherford backscattering spectrometry, and the optoelectronic properties by current-voltage and photoluminescence measurements. The extent of band bending at the cluster-ZnO interface was quantitatively modeled through numerical simulations. The decoration of ZnO nanorods with monometallic Au or Pt nanoclusters causes a significant depletion of free electrons below the surface, leading to a reduction of UV photoluminescence, an increase of ZnO nanorod dark resistance (up to 200 times) and, as a consequence, an improved sensitivity (up to 6 times) to UV light. These effects are strongly enhanced (up to 450 and 10 times, respectively) when ZnO nanorods are decorated with bimetallic AuPt nanoclusters that substantially augment the depletion of free carriers likely due to a more efficient absorption of the gas molecules on the surface of the bimetallic AuPt nanoclusters than on that of their monometallic counterparts. The depletion of free carriers in cluster decorated ZnO nanorods is quantitatively investigated and modelled, allowing the application of these composite materials in UV sensing and light induced catalysis. ispartof: NANOSCALE vol:12 issue:37 pages:19213-19222 ispartof: location:England status: published

There is a huge demand for rapid, reliable and low-cost methods for the analysis of heavy metals in drinking water, particularly in the range of sub-part per billion (ppb). In the present work, we describe the preparation, characterization and analytical performance of the disposable sensor to be employed in Square Wave Anodic Stripping Voltammetry (SWASV) for ultra-trace simultaneous determination of cadmium and lead. The electrode consists of graphene paper-perfluorosulfonic ionomer-bismuth nano-composite material. The electrode preparation implies a key step aimed to enhance the Bi3+ adsorption into nafion film, prior to the bismuth electro-deposition. Finely dispersed bismuth nanoparticles embedded in the ionomer film are obtained. The electrode was characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX), Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and Electrochemical Impedance Spectroscopy (EIS). The electrode shows a linear response in the 5&ndash, 100 ppb range, a time-stability tested up to almost three months, and detection limits up to 0.1 ppb for both Pb2+ and Cd2+. The electrode preparation method is simple and low in cost and the obtained analytical performance is very competitive with the state of art for the SWASV determination of Pb2+ and Cd2+ in solution.

Zinc oxide (ZnO) nanostructures were synthesized in the form of nanoparticles, nanoflowers and nanourchins. Structural, electronic and optical characterization of the samples was performed via standard techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence, Raman and ultraviolet-visible (UV-Vis) spectroscopy. Point defect structures which are specific to each morphology have been investigated in terms of their concentration and location via state-of-the-art electron paramagnetic resonance (EPR) spectroscopy. According to the core-shell model, all the samples revealed core defects; however, the defects on the surface are smeared out. Finally, all three morphologies have been tested as electrode materials in a real supercapacitor device and the performance of the device, in particular, the specific capacitance and the storage mechanism, has been mediated by the point defects. Morphology-dependent defective ZnO electrodes enable the monitoring of the working principle of the supercapacitor device ranging from electric double-layer capacitors (EDLC) to pseudo-supercapacitors. © 2020 The Royal Society of Chemistry.

Earth-abundant materials for electrochemical water splitting typically show a lower efficiency than noble and rare metal electrocatalysts. Nanostructuring and appropriate material design can largely improve the performances of low-cost electrocatalysts, opening the route towards profitable mass production. Here, we report on a quantitative investigation of the oxygen evolution reaction (OER) on Ni-based nanowall (NW) electrodes. The NiO and Ni(OH)2 NW films (200 or 400 nm thick) are produced by chemical bath deposition followed by calcination at 350 °C. The morphology and the chemical arrangement of the NW were studied, before and after the OER, by scanning electron microscopy, energy dispersive X-ray analysis and X-ray photoelectron spectroscopy. The OER electrocatalytic activity was investigated by electrochemical measurements under alkaline conditions (1 M KOH), demonstrating a stable overpotential of 345 mV at 10 mA cm−2, a Tafel slope of 48 mV dec−1 and an O2 turnover conversion frequency (TOF) of up to 0.18 s−1. The quantitative measurement of active electrocatalysts, through cross-correlation of the experimental data, shows nearly 100% material utilization in the 200 nm NiO NW. In thicker NiO or Ni(OH)2 NW films this fraction decreases below 60%, probably due to the decrease in the electric potential along the nanostructure, as revealed by numerical simulation. These data and discussion support the use of low-cost Ni-based nanostructures for high-efficiency and sustainable electrocatalysts.

Nanostructured WO3 represents a promising material for electrochromic and sensing devices. In this scenario, electrodeposition is a promising low-cost approach for careful production. The electrodeposition of tungsten oxide film from a peroxo-tungstic-acid (PTA) solution is investigated. WO3 is synthetized onto Indium doped Tin Oxide (ITO) substrates, in a variety of shapes, from a fragmentary, thin layer up to a thick continuous film. Samples were investigated by scanning electron (SEM) and atomic force microscopy (AFM), Rutherford backscattering spectrometry (RBS), X-ray Diffraction analysis (XRD), energy gap measurement. Electrodeposition current curves are compared with characterization results to model the growth process. Early stages of electrodeposition are characterized by a transient cathodic current revealing an instantaneous nucleation followed by a diffusion limited process. A quantitative analysis of W deposition rate and current at working electrode validates a microscopic model for WO3 electrodeposition driving the process towards nanostructured versus continuous WO3 film.

Zinc Oxide (ZnO) nanowalls (NWLs) are interesting nanostructures for sensing application. In order to push towards the realization of room-temperature operating sensors, a detailed investigation of the synthesis effect on the electrical and optical properties is needed. This work focuses on the low-cost synthesis of ZnO NWLs by means of chemical bath deposition (growth time of 5, 60, and 120 minutes) followed by annealing in inert ambient (temperature of 100, 200, and 300 &deg, C). The as-grown NWLs show a typical intertwined network of vertical sheets whose features (thickness and height) stabilize after 60 minutes growth. During thermal annealing, NWLs are converted into ZnO. The electric transport across the ZnO NWL network radically changes after annealing. A higher resistivity was observed for longer deposition times and for higher annealing temperatures, at which the photoluminescence spectra resemble those obtained for ZnO material. A longer deposition time allows for a better transformation to ZnO during the annealing, thanks to the presence of ZnO seeds just after the growth. These findings can have a significant role in promoting the realization of room-temperature operating sensors based on ZnO NWLs.

Energy storage performances of Ni-based electrodes rely mainly on the peculiar nanomaterial design. In this work, a novel and low-cost approach to fabricate a promising core-shell battery-like electrode is presented. Ni(OH)2@Ni core-shell nanochains were obtained by an electrochemical oxidation of a 3D nanoporous Ni film grown by chemical bath deposition and thermal annealing. This innovative nanostructure demonstrated remarkable charge storage ability in terms of capacity (237 mAh g−1 at 1 A g−1) and rate capability (76% at 16 A g−1, 32% at 64 A g−1). The relationships between electrochemical properties and core-shell architecture were investigated and modelled. The high-conductivity Ni core provides low electrode resistance and excellent electron transport from Ni(OH)2 shell to the current collector, resulting in improved capacity and rate capability. The reported preparation method and unique electrochemical behaviour of Ni(OH)2@Ni core-shell nanochains show potential in many field, including hybrid supercapacitors, batteries, electrochemical (bio)sensing, gas sensing and photocatalysis.

Energy storage performances of Ni-based electrodes rely mainly on the peculiar nanomaterial design. In this work, a novel and low-cost approach to fabricate a promising core-shell battery-like electrode is presented. Ni(OH)2@Ni core-shell nanochains were obtained by an electrochemical oxidation of a 3D nanoporous Ni film grown by chemical bath deposition and thermal annealing. This innovative nanostructure demonstrated remarkable charge storage ability in terms of capacity (237 mAh g−1 at 1 A g−1) and rate capability (76% at 16 A g−1, 32% at 64 A g−1). The relationships between electrochemical properties and core-shell architecture were investigated and modelled. The high-conductivity Ni core provides low electrode resistance and excellent electron transport from Ni(OH)2 shell to the current collector, resulting in improved capacity and rate capability. The reported preparation method and unique electrochemical behaviour of Ni(OH)2@Ni core-shell nanochains show potential in many field, including hybrid supercapacitors, batteries, electrochemical (bio)sensing, gas sensing and photocatalysis.

The massive production of nanostructures with controlled features and high surface area is a challenging and timely task in view of developing effective materials for sensing and catalysis. Herein, functional ZnO nanostructures, named microflowers (MFs) have been prepared by a facile and rapid chemical bath deposition. ZnO MFs show an intriguing sheets-composed spheroidal shape, with diameters in the range 0.2&ndash, 2.5 &micro, m, whose formation is achieved by a complexing action by F in an aqueous solution of zinc nitrate hexahydrate and hexamethylenetetramine. The evolution of the physical and structural properties of the material, following post-deposition thermal annealing, has been investigated by scanning electron microscopy (SEM), energy dispersive X-ray analyses (EDX), photoluminescence (PL) and X-ray diffraction (XRD) techniques. The effectiveness of ZnO MFs in UV detection has also been tested to account for the potentiality of these nanostructures.

A novel electrochemical device based on Nickel oxide sensing species is described. The miniaturized device contains three integrated metal microelectrodes with the working active electrode made of Ni zero-valence. It has been proved to be sensitive and versatile in the detection of glucose on saliva. The findings here reported pay the way to future development of versatile portable sensors addressing easy-to-use and low-cost system.

A novel Ni nanofoam electrode has been fabricated by low-cost methods and applied for non-enzymatic glucose sensing. Ni(OH)2 nanowalls, prepared by room-temperature chemical bath deposition, were transformed into an ensemble of Ni nanoparticles (20–30 nm in size) upon annealing in forming gas at 350 °C, and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), temperature programmed reduction with hydrogen (H2-TPR) and surface area measurements. The Ni nanofoam was converted to the catalytic Ni(OH)2/NiOOH – necessary for non-enzymatic glucose oxidation – by cyclic voltammetry (CV) in NaOH electrolyte. The electrode fabricated on conducting glass substrate showed a glucose sensitivity of 2.37 mA/cm2 mM, a linear range of 0.01–0.7 mM, a limit of detection (LOD) of 5 μM, a fast response time (1 s), and resistance to chloride poisoning. The glucose sensor also exhibited an excellent long-term stability (4% decrease in sensitivity after 64 days) and selectivity in the presence of common interfering species. The versatility of the preparation method was demonstrated in the fabrication of a flexible (plastic substrate) sensor with a sensitivity of 1.43 mA/cm2 mM. The ease of fabrication and the excellent properties of Ni nanofoam in glucose sensing make it promising for low-cost and wearable sensing applications.

Visible luminescence from ZnO nanorods (NRs) is attracting large scientific interest for light emission and sensing applications. We study visible luminescent defects in ZnO NRs as a function of post growth thermal treatments, and find four distinct visible deep level defect states (VDLSs): blue (2.52 eV), green (2.23 eV), orange (2.03 eV), and red (1.92 eV). Photoluminescence (PL) studies reveal a distinct modification in the UV (3.25 eV) emission intensity and a shift in the visible spectra after annealing. Annealing at 600 degrees C in Ar (Ar600) and O-2 (O600) causes a blue and red-shift in the visible emission band, respectively. All samples demonstrate orange emission from the core of the NR, with an additional surface related green, blue, and red emission in the As-Prep, Ar600, and O600 samples, respectively. From PL excitation (PLE) measurements we determine the onset energy for population of the various VDLSs, and relate it to the presence of an Urbach tail below the conduction band due to a presence of ionized Zn-i or Zn-i complexes. We measured an onset energy of 3.25 eV for the as prepared sample. The onset energy red-shifts in the annealed samples by about 0.05 to 0.1 eV indicating a change in the defect structure, which we relate to the shift in the visible emission. We then used X-ray photoemission spectroscopy (XPS), and elastic recoil detection analysis (ERDA) to understand changes in the surface structure, and H content, respectively. The results of the XPS and ERDA analysis explain how the chemical states are modified due to annealing. We summarize our results by correlating our VDLSs with specific intrinsic defect states to build a model for PL emission in ZnO NRs. These results are important for understanding how to control defect related visible emission for sensing and electroluminescence applications.

Hierarchical nanostructures composed of Ni(OH)2 nanoflakes on ZnO nanorods (NRs) are fabricated by a low-cost, fully chemical method at room-temperature. The morphological features of the ZnO NRs were varied (by changing the chemical bath deposition parameters) in terms of height and lateral size. ZnO NRs provide a large surface area substrate for the pulsed electrodeposition of nanostructured Ni(OH)2. The correlation between the synthetic parameters, the final structure and the electrochemical behavior of Ni(OH)2/ZnO nanostructures is investigated. The enzyme-free oxidation of glucose at the surface of electrodeposited Ni(OH)2 is demonstrated in 0.1 M NaOH, revealing that a proper choice of the electrodes fabrication conditions improves the glucose sensitivity up to 1.85 mA cm−2 mM−1, with a linear detection range of 0.04–2.10 mM. All the samples show a fast response time (less than 1 s), resistance in chloride solution, selectivity in the presence of common interfering electroactive species and excellent long-term stability. All these features, combined with the ease of the fabrication method, make Ni(OH)2/ZnO nanostructures an ideal alternative for inexpensive amperometric glucose sensing applications.

NiO nanowalls were grown by low-cost chemical bath deposition (CBD) method and thermal annealing. SEM analysis showed a high surface area and porous thin film formed by a network of ~20 nm thick and ~270 nm tall nanosheets. NiO nanowalls were prepared onto interdigitated electrodes and applied for acetone sensing. The response transients at various temperatures were recorded an successfully modelled by two adsorption sites. Both sites are active below 250 °C, while only the site with shorter response time is active above 250 °C. At the optimal temperature of 250 °C, the sensor demonstrated high sensitivity to acetone (1–40 ppm), a low limit of detection (LoD) of ~200 ppb and good selectivity. These unique features combined with the low-cost and simple fabrication process make it a cheap and efficient acetone sensor.

NiO-based NO2 sensors operating at room temperature are attracting great attentions due to their promising energy and cost saving performances. However, only a few reports showed high sensitivity and selectivity in the sub-ppm concentration range and low limit of detection (LoD). In this work, we designed and fabricated by a low-cost chemical bath deposition (CBD) and thermal annealing a nanostructured and porous NiO thin film (nanoporous NiO film) composed of NiO nanoparticles (30−50 nm). The nanoporous NiO film was then applied as sensing element for the NO2 detection at room temperature, demonstrating a high response to sub-ppm level NO2 (140 ppb), excellent selectivity and stability, and a very low LoD of 20 ppb. The NO2 sensing mechanism was investigated and satisfactorily modelled by two energetically different and independent adsorption sites at room temperature. Both sites contribute to the NO2 detection at room temperature while only one site contributes at higher temperatures. The described low-cost fabrication method and the discussed superior NO2 sensing performances at room temperature make the nanoporous NiO film a promising NO2 sensor for environmental monitoring.

Correction for ‘High intrinsic activity of the oxygen evolution reaction in low-cost NiO nanowall electrocatalysts’ by Salvatore Cosentino et al., Mater. Adv., 2020, DOI: 10.1039/d0ma00467g.

ZnO nanowalls (NWLs) represent a non-toxic, Earth abundant, high surface-to-volume ratio, semiconducting nanostructure which has already showed potential applications in biosensing, environmental monitoring and energy. Low-cost synthesis of these nanostructures is extremely appealing for large scale upgrading of laboratory results, and its implementation has to be tested at the nanoscale, at least in terms of chemical purity and crystallographic orientation. Here, we have produced pure and texturized ZnO NWLs by using chemical bath deposition (CBD) synthesis followed by a thermal treatment at 300 °C. We examined the NWL formation process and the new obtained structure at the nanoscale, by means of scanning and transmission electron microscopy in combination with x-ray diffraction and Rutherford backscattering spectrometry. We have shown that only after annealing at 300 °C in nitrogen does the as-grown material, composed of a mixture of Zn compounds NWLs, show its peculiar crystal arrangement. The resulting ZnO sheets are in fact made by ZnO wurtzite domains (4-5 nm) that show a particular kind of texturization; indeed, they are aligned with their own c-axis always perpendicular to the sheets forming the wall and rotated (around the c-axis) by multiples of 20° from each other. The presented data show that low-cost CBD, followed by an annealing process, gives pure ZnO with a peculiarly ordered nanostructure that shows three-fold symmetry. Such evidence at the nanoscale will have significant implications for realizing sensing or catalyst devices based on ZnO NWLs.

The vapochromic and chemiresistive properties of a nanofibrillar molecular material composed of an amphiphilic ZnII Schiff-base complex, 1, are explored with the aim to obtain new materials with multifunctional properties. The solid 1 is characterized by the existence of two stable dimorphs, both exhibiting a nanofibrillar morphology. The thermal annealing of the ground solid 1 induces an irreversible lamellar-to-square columnar structural phase transition, as assessed by differential scanning calorimetry and X-ray diffraction analysis. When exposed to vapours of a Lewis base, spin coated films of the square columnar dimorph exhibit a marked change of both the optical absorption spectrum and the resistance, because of chemisorption of the Lewis base with the formation of 1·Lewis base adducts. The chemisorbed material is easily restored by thermal heating (150 °C), inducing desorption of the Lewis base. The changes of the properties are reproducible in successive cycles of exposure/restoring. Therefore, the present contribution provides new insights into the properties of this molecular material, potentially useful as a sensor for volatile organic Lewis bases.

This work focuses on the synthesis and gas sensing properties of ZnO nanowalls (ZnO NWLs) grown by a simple cheap chemical bath deposition method on a thin layer of aluminum (about 20 nm thick) printed on the Pt interdigitated electrodes area of conductometric alumina platforms. Post-deposition annealing in nitrogen atmosphere at 300 °C enabled the formation of a ZnO intertwined 2D foils network. A wide characterization was carried out to investigate the composition, morphology and microstructure of the nanowalls layer formed. The gas sensing properties of the films were studied by measuring the changes of electrical resistance upon exposure to low concentrations of carbon monoxide (CO) and nitrogen dioxide (NO2) in air. The sensor response to CO or NO2 was found to be strongly dependent on the operating temperature, providing a means to tailor the sensitivity and selectivity toward these selected target gases.