The ZnO-NiO nano-composite: A brief characterization,kinetic and thermodynamic study and study the Arrhenius model on the sulfasalazine photodegradation

The coupled ZnO–NiO nano-composite (NC) was prepared and identified by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), UV–Vis diffuse reflection spectroscopy (DRS) and Fourier transformation infrared spectroscopy (FTIR) characterization techniques. The crystallite sizes of about 6.7, 36.7 and 29.5 nm were obtained for the NiO, ZnO, and ZnO/NiO samples by the Williamson-Hall equation, and about of 33.5, 33.8 and 39.8 nm by the Scherrer equation, respectively. The energy dispersive X-Ray analysis (EDX) showed a NiO:ZnO mole ratio of 3.1 for the composite. The band gap energies of 3.49, 3.19, and 3.02 eV were estimated for the NiO, ZnO, and ZnO–NiO samples by using the absorption edge wavelengths of 355, 388, and 410, respectively. The pHpzc values of 9.3, 8.8, and 7.6 were also estimated for the NiO, ZnO, and ZnO–NiO samples respectively. At initial steps of the work about 42%, 60%, and 87% of a 10 mg/L SZ solution were degraded by the ZnO and NiO NPs and the ZnO–NiO NC, respectively. The best photocatalytic activity was obtained at pH 6.5 (near the pHpzc: 7.6), 0.7 g/L of the catalyst, and 7 mg/L sulfasalazine (SZ). The rate constants of 0.0904 min⁻¹ (t_1/2 = 7.66 min) and 0.0915 min⁻¹ (t_1/2 = 7.57 min) were obtained for the SZ photodegradation and mineralization processes, respectively. The frequency factor of 2.131 × 10⁴ min⁻¹ and the activation energy of 15.87 kJ/mol were obtained for the process by the Arrhenius equation. A negative activation ΔS (−0.22 kJ/mol) with the positive ΔH and ΔG values obtained for the SZ photodegradation by the ZnO–NiO composite.     

Preparation of ZnO nanoparticles and nanosheets and their application to dye-sensitized solar cells

ZnO nanoparticles which have diameter of 15 nm were prepared by hydrothermal method. ZnO nanosheets were obtained by re-hydrothermal treatment of ZnO nanoparticles. The phase and morphology were investigated by using transmission electron microscope, scanning electron microscope and X-ray diffraction. Also, absorbance spectra were measured by using a UV–vis spectrophotometer. A fill factor of 0.55, short-circuit current of 2.059 mA/cm², open-circuit voltage of 0.593 V and an overall light to electricity conversion efficiency of 1.55% for the solar cell based on ZnO nanosheets were obtained.     

Pt–NiO nanophase electrodes for dye-sensitized solar cells

A new type of counter electrode comprising of Pt and NiO biphase was prepared an RF magnetron cosputtering system for a dye-sensitized solar cell (DSSC). Transmission electron microscope images, transmission electron diffraction patterns, and X-ray diffraction patterns of the Pt–NiO electrodes confirmed the formation of a nanosized Pt polycrystalline phase of 7 nm mixed with porous amorphous NiO phase. The short-circuit current density and cell efficiency were increased from 0.22 to 0.30 mA/cm² and from 2.1% to 2.8%, respectively, and almost constant open-circuit voltage and fill factor, 0.53 V and 63%, respectively, were observed.     

High-temperature optical properties and stability of AlxOy–AlNx–Al solar selective absorbing surface prepared by DC magnetron reactive sputtering

Al_xO_y–AlN_x–Al selective absorbing surface was prepared by DC magnetron reactive sputtering with aluminum alloy (LY13)¹ in air and argon. The studies were carried out to access the high-temperature (400°C–600°C) optical properties and stability of the coatings. The coatings were found to withstand heating at 600°C for 30 min in 4.5×10⁻³ Pa vacuum with absorptance 0.94 and emittance 0.07 after annealing. After heating at 450°C for 10 h, the specimen still had good performance whose absorptance and emittance was 0.93 and 0.07, respectively. Auger electron spectroscopy was used to analyse the structure of the solar selective surface before and after annealing.     

Sol–gel derived CuCoMnOx spinel coatings for solar absorbers: Structural and optical properties

A novel black coloured coating with the composition CuCoMnO_x was prepared using sol–gel synthesis. The coatings were deposited using the dip-coating technique from alcoholic sols based on Mn-acetate and Co- and Cu-chloride precursors. Thermogravimetric analysis showed that xerogels become crystalline at 316°C while X-ray diffraction analysis revealed that the coatings and powders correspond predominantly to CuCoMnO_x spinels. Rutherford back scattering (RBS) and transmission electron microscopic (TEM) studies combined with energy dispersive X-ray spectroscopy (EDXS) measurements confirmed that Cu, Mn and Co are present in the films in stoichiometric ratios close to that in the initial sols. IR spectroscopy has been employed to study the formation of sols by following the changes in the vibrational bands of the acetate groups during both thermal hydrolysis and the ageing of sols to xerogels. It was found that ageing of xerogels was accompanied by the formation of −COO⁻ bridging units, which at 250°C are no longer visible in the IR spectra but substituted by the vibrational modes characteristic for CuCoMnO_x. The solar absorptance (a_s) and thermal emittance (e_T) of the coatings when deposited on an Al-substrate are a_s=0.9 and e_T=0.05, which rank deposited black sol–gel CuCoMnO_x spinels among the promising candidates for spectrally selective absorber coatings for solar collectors and solar facades.     

Characterisation of high-temperature-resistant spectrally selective paints for solar absorbers

The spectrally selective paint coatings were prepared from organically modified siloxane resin and inorganic pigment (FeMnCuO_x-P320). To optimise the low-emittance properties, different thicknesses of paints were applied on high-reflecting Al foil by a draw bar coater. For all paints, optical and thermal properties were determined as well as their adhesion resistance. Pigment to volume concentration ratio was 20% and for thicknesses of about 1.7–2.0 g/m², the solar absorptance for these samples were a_s=0.90–0.92 with corresponding thermal emittance of e_T=0.20–0.25. Temperature stability of these samples was followed by FT-IR spectroscopy at 300°C. The obtained results indicated good temperature stability of prepared paint coatings.     

Nanostructured solar cell based on spray pyrolysis deposited ZnO nanorod array

In this paper we present a realization of an extremely thin absorber (ETA) layer solar cell by the chemical spray pyrolysis method. CuInS₂ absorber was deposited onto a blocking layer coated ZnO nanorods grown on a transparent conductive oxide. Layers and cells were characterized by optical and Raman spectroscopy, and scanning electron microscopy. Current–voltage, spectral response and electron beam induced current measurements were applied to solar cells. ZnO nanorod cell showed twice higher short circuit current density than the flat reference. ETA cells with efficiency of 2.2% (j=12 mA/cm², V_oc=425 mV, FF=43%) and of 2.5% were prepared using TiO₂-anatase and an indium sulfide blocking layer, respectively.     

Microcrystalline silicon thin film solar modules on glass

We developed microcrystalline silicon (μc-Si:H) thin film solar modules on textured ZnO-coated glass. The single junction (p–i–n) cell structure was prepared by plasma-enhanced chemical vapour deposition (PECVD) at substrate temperatures below 250 °C. Front ZnO and back contacts were prepared by sputtering. A process for the monolithic series connection of μc-Si:H cells by laser scribing was developed. These microcrystalline p–i–n modules showed aperture area efficiencies up to 8.3% and 7.3% on aperture areas of 64 and 676 cm², respectively. The temperature coefficient of the efficiency was −0.4%/K.     

TEM and EELS microanalysis of pc-Si thin film solar cells deposited by means of HW CVD

A p–i–n doped pc-silicon thin film grown by means of hot wire chemical vapour deposition (HW CVD) on a zinc oxide film has been investigated by transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). The structure of both layers, the ZnO substrate layer as much as the silicon thin film and the chemical composition at the interface were the subjects of our investigations. We found that a file of pure silicon with a thickness of about 5 nm covers the substrate surface. A plausible model for getting information on the wavyness of the interface ZnO/pc-Si and the thickness of this pure Si-layer was developed.     

Microcrystalline silicon and the impact on micromorph tandem solar cells

Intrinsic microcrystalline silicon opens up new ways for silicon thin-film multi-junction solar cells, the most promising being the “micromorph” tandem concept. The microstructure of entirely microcrystalline p–i–n solar cells is investigated by transmission electron microscopy. By applying low pressure chemical vapor deposition ZnO as front TCO in p–i–n configurated micromorph tandems, a remarkable reduction of the microcrystalline bottom cell thickness is achieved. Micromorph tandem cells with high open circuit voltages of 1.413 V could be accomplished. A stabilized efficiency of around 11% is estimated for micromorph tandems consisting of 2 μm thick bottom cells. Applying the monolithic series connection, a micromorph module (23.3 cm²) of 9.1% stabilized efficiency could be obtained.     

Kinetics of the hydrogen evolution reaction on Ni-(Ebonex-supported Ru) composite coatings in alkaline solution

The hydrogen evolution reaction (HER) was studied on Ni, Ni-Ebonex and Ni-(Ebonex-Ru) coatings in 1 mol dm⁻³ NaOH solution at 25 °C. The composite coatings were electrodeposited from a nickel Watts-type bath containing suspended Ebonex (chemical composition mainly Ti₄O₇) or Ebonex-supported Ru(10 wt.%) particles (0–10 g dm⁻³) onto Ni 40 mesh substrate. The electrodes were investigated by cyclic voltammetry (CV), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) in combination with energy dispersive X-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS), electrochemical impedance spectroscopy (EIS) and polarization measurements. These investigations showed that the roughness factor of the Ni-(Ebonex-Ru) and the Ni-Ebonex coating was 29 and 6 times higher than that of a pure Ni coating, respectively. In the whole potential range of the HER only one Tafel slope of about −120 mV was present at the polarization curves of Ni and Ni-Ebonex electrodes, with increased activity of the latter being attributed only to the increase of the electrochemically active surface area. The Ni-(Ebonex-Ru) electrodes exhibited the highest intrinsic catalytic activity with two Tafel slopes, indicating also that the HER takes place exclusively on Ru active sites.     

Electrodeposition zinc-oxide inverse opal and its application in hybrid photovoltaics

This article reports the preparation of three-dimensional (3D) mesoporous zinc oxide (ZnO) films and their application in solar cells. The films were obtained through electrochemical deposition in DMSO solutions by using PS colloidal crystal as templates. The ZnO films with inverse opal (IO) structure were obtained after removing the templates by thermolysis. The ordered porous ZnO films were used to prepare hybrid solar cells by infiltrating the films with poly(3-hexylthiophene) (P3HT) or P3HT:ZnO nanocomposite. Results showed that the interpenetrating network of both ZnO(IO) and P3HT can form continuous pathways for electron and hole transport. By infiltrating a P3HT:ZnO nanocomposite into the porous ZnO films, the photocurrent of the solar cell can be dramatically improved. The cell shows the V_oc and I_sc of 462 mV and 444.3 μA/cm², respectively. By using a 420 nm cutoff filter, the cell retains about 80% and 50% of its original V_oc and I_sc after continuous white-light illumination (100 mW/cm²) for 10 h. Stability of the device under above conditions was estimated to be 51 h.     

Antireflective coating fabricated by chemical deposition of ZnO for spherical Si solar cells

ZnO thin films as an antireflective (AR) coating have been successfully fabricated on spherical Si solar cells by chemical deposition, which enables uniform film formation. ZnO films were prepared chemically by immersing the cell in an aqueous solution of zinc nitrate and dimethylamineborane maintained at 80 °C. The current–voltage measurements of the solar cells confirmed the increase in short circuit current induced by the AR effect. The open circuit voltage and fill factor were improved by surface passivation. As a result, the conversion efficiency of cells without an AR coating (9.45%) increased to 11.8%, which represents a 25% (relative) increase. The results indicate that the chemical deposition of ZnO is effective for the AR coating of spherical Si solar cells.     

High performance W–AlN cermet solar coatings designed by modelling calculations and deposited by DC magnetron sputtering

High solar performance W–AlN cermet solar coatings were designed using a numerical computer model and deposited experimentally. In the numerical calculations aluminium oxynitride (AlON) was used as ceramic component. The dielectric function and then complex refractive index of W–AlON cermet materials were calculated using the Sheng's approximation. The layer thickness and W metal volume fraction were optimised to achieve maximum photo-thermal conversion efficiency for W–AlON cermet solar coatings on an Al reflector with a surface AlON ceramic anti-reflection layer. Optimisation calculations show that the W–AlON cermet solar coatings with two and three cermet layers have nearly identical solar absorptance, emittance and photo-thermal conversion efficiency that are much better than those for films with one cermet layer. The optimised calculated AlON/W–AlON/Al solar coating film with two cermet layers has a high solar absorptance of 0.953 and a low hemispherical emittance of 0.051 at 80°C for a concentration factor of 2. The AlN/W–AlN/Al solar selective coatings with two cermet layers were deposited using two metal target direct current magnetron sputtering technology. During the deposition of W–AlN cermet layer, both Al and W targets were run simultaneously in a gas mixture of argon and nitrogen. By substrate rotation a multi-sub-layer system consisting of alternating AlN ceramic and W metallic sub-layers was deposited that can be considered as a macro-homogeneous W–AlN cermet layer. A solar absorptance of 0.955 and nearly normal emittance of 0.056 at 80°C have been achieved for deposited W–AlN cermet solar coatings.     

High flux photochemical changes in Black Chrome solar absorbing coatings

Black Chrome samples have been exposed to concentrated solar radiation (350kW m⁻²–2.5 MW m⁻²) at elevated temperatures (250–500°C) over limited periods of time with the resultant observation that the coatings degrade less optically than equivalent coatings heated by IR radiation. The decreased degradation is a result of decreased oxidation of the Black Chrome coating under solar heating as compared to oven heating. This is proposed to be due to photo-desorption of gaseous oxygen bearing species from the surface of the film.     

Optical and morphological characterisation of low refractive index materials for coatings on solar collector glazing

Nanostructured coatings based on the elements Si, O, Mg, and F have been deposited as thin films by sol–gel dip-coating in a particle-free atmosphere. The refractive index of the prepared SiO₂ and quaternary Mg–F–Si–O thin films has been determined from spectrophotometric and ellipsometric data. The morphology of those thin films has been observed by TEM.Nanoporous SiO₂ coatings with a pore size smaller than 3 nm (TEM) and a pore volume fraction of 30% (as inferred from ellipsometric measurements) have been achieved. They are characterised by significantly lower refractive index values (approx. 1.32 at 550 nm) than compact SiO₂ (approx. 1.46).Quaternary Mg–F–Si–O thin films are characterised by a surprisingly low refractive index (approx. 1.26 at 550 nm), even lower than that of dense MgF₂ coatings (approx. 1.38). Preliminary results of transmission electron microscopy suggest that these films are of nanocomposite nature.In both cases, highly transparent samples have been produced in a single dip-coating step followed by simple thermal annealing in air. Broad spectral transmittance maxima are observed exceeding values of 98.5% (nanoporous SiO₂) and 99.5% (quaternary Mg–F–Si–O films).The quaternary films might exhibit a higher ageing stability than porous SiO₂ films with respect to pore-filling and could therefore be a promising alternative for single-layered anti-reflection coatings as well as for multi-layered coloured coatings on solar collector glazing.     

Temperature effect on the electrical properties of undoped NiO thin films

Undoped NiO thin films have been prepared onto glass substrate by e-beam evaporation of the element Ni in vacuum at 2 × 10⁻⁴ Pa. The as-deposited Ni films were then oxidized in air by heating about 2 h at a temperature of 470 K and then the oxidized Ni films are turned into NiO thin films. From the deposition time and film thickness after annealing in air, an effective deposition rate of NiO thin films was about 6.67 nms⁻¹. X-ray diffraction (XRD) study shows the NiO films are amorphous in nature. SEM studies of the surface morphology of NiO films exhibit a smooth and homogeneous growth on the entire surface. The elemental composition of NiO films is estimated by Energy Dispersive Analysis of X-rays (EDAX) method. The effects of temperature on the electrical properties of NiO thin films were studied in details. The heating and cooling cycles of the samples are reversible in the investigated temperature range after successive heat-treatment in air. Thickness dependence of conductivity is well in conformity with the Fuchs–Sondheimer theory. Temperature dependence of electrical conductivity shows a semiconducting behavior with activation energy. The thickness dependence of activation energy as well as thermopower studies was done within 293–473 K temperature range, respectively. Thermopower study indicates the NiO films a p-type semiconductor. Optical study in the wavelength range 0.3 < λ<1.2 μm range exhibits a high transmittance in the visible as well as in the near infra-red. Calculation from the optical data, the NiO sample exhibits a band gap at 3.11 eV, which does agree well with earlier reported values. These studies may be of importance for the application of this material in energy efficient surface coating devices.     

Sol–gel deposited nickel oxide films for electrochromic applications

The electrochromic (EC) behavior, the microstructure, and the morphology of sol–gel deposited nickel oxide (NiO_x) coatings were investigated. The films were produced by spin and dip-coating techniques on indium tin oxide (ITO)/glass and Corning glass (2947) substrates.The coating solutions were prepared by reacting nickel(II) 2-ethylhexanoate as the precursor, and isopropanol as the solvent. NiO_x was heat treated at 350 °C for 1 h. The surface morphology, crystal structure, and EC characteristics of the coatings were investigated by scanning electron microscopy (SEM), electron dispersive spectroscopy (EDS), atomic force spectroscopy (AFM), X-ray diffractometry (XRD), and cyclic voltammetry (CV).SEM and AFM images revealed that the surface morphology and surface characteristics of the spin- and dip-coated films on both types of substrate were different. XRD spectra revealed that both films were amorphous, either on ITO or Corning glass substrates. CV showed a reversible electrochemical insertion or extraction of the K⁺ ions, cycled in 1 M KOH electrolyte, in both type of film. The crystal structure of the cycled films was found to be XRD amorphous. Spectroelectrochemistry demonstrated that dip-coated films were more stable up to 1000 coloration–bleaching cycles, whereas spin-coated films gradually degraded after 500 cycles.     

Silicon and solar-grade silicon production by solar dissociation of Si3N4

The temperature required for carbothermal reduction of silica—in the range 2100–2300 °C—is past the upper limit for combustion process heat. It is therefore an interesting candidate for solar–thermal processing. The production of solar-grade silicon from carbothermally produced silicon requires an energy-intensive long-duree high-temperature purification process. We propose here a two-step solar process for the production of silicon from silica: first, a carbothermal reduction in the presence of nitrogen to yield silicon nitride and second, the solar dissociation of the nitride to yield silicon. This last step could be combined with purification of the silicon if solar-grade silicon is the desired end-product. In this paper, we report on experimental results that indicate that silicon nitride can be dissociated to yield silicon with no detectable nitride content.     

Solar chemical reactor technology for industrial production of lime

We developed the solar chemical reactor technology to effect the endothermic calcination reaction CaCO₃(s) → CaO(s) + CO₂(g) at 1200–1400 K. The indirect heating 10 kW_th multi-tube rotary kiln prototype processed 1–5 mm limestone particles, producing high purity lime that is not contaminated with combustion by-products. The quality of the solar produced quicklime meets highest industrial standards in terms of reactivity (low, medium, and high) and degree of calcination (exceeding 98%). The reactor’s efficiency, defined as the enthalpy of the calcination reaction at ambient temperature (3184 kJ kg⁻¹) divided by the solar energy input, reached 30–35% for quicklime production rates up to 4 kg h⁻¹. The solar lime reactor prototype operated reliably for more than 100 h at solar flux inputs of about 2000 kW m⁻², withstanding the thermal shocks that occur in solar high temperature applications. By substituting concentrated solar energy for fossil fuels as the source of process heat, one can reduce by 20% the CO₂ emissions in a state-of-the-art lime plant and by 40% in a conventional cement plant. The cost of solar lime produced in a 20 MW_th industrial solar calcination plant is estimated in the range 131–158 $/t, i.e. about 2–3 times the current selling price of conventional lime.