Enhancement of optical and electrical properties of SILAR deposited ZnO thin films through fluorine doping and vacuum annealing for photovoltaic applications

Undoped and fluorine doped ZnO thin films were deposited onto glass substrates using successive ionic layer adsorption and reaction (SILAR) technique and then annealed at 350 °C in vacuum ambience. The F doping level was varied from 0 to 15 at% in steps of 5 at%. The XRD analysis showed that all the films are polycrystalline with hexagonal wurtzite structure and preferentially oriented along the (002) plane. Crystallite sizes were found to increase when 5 at% of F is doped and then decreased with further doping. It was seen from the SEM images that the doping causes remarkable changes in the surface morphology and the annealing treatment results in well-defined grains with an improvement in the grain size irrespective of doping level. All the films exhibit good transparency (>70%) after vacuum annealing. Electrical resistivity of the film was found to be minimum (1.32×10⁻³ Ω cm) when the fluorine doping level was 5 at%.     

Studies on influence of hydrogen and carbon monoxide concentration on reduction progression behavior of molybdenum oxide catalyst

Temperature programmed reduction (TPR) analysis was applied to investigate the chemical reduction progression behavior of molybdenum oxide (MoO₃) catalyst. The composition and morphology of the reduced phases were characterized by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM). The reduction progression of MoO₃ catalyst was attained with different reductant types and concentration (10% H₂/N₂, 10% and 20% CO/N₂ (%, v/v)). Two different modes of reduction process were applied. The first approach of reduction involved non-isothermal mode reduction up to 700 °C, while the second approach of reduction involved the isothermal mode reduction for 60 min at 700 °C. Hydrogen temperature programmed reduction (H₂-TPR) results showed the reduction progression of three-stage reduction of MoO₃ (Mo⁶⁺ → Mo⁵⁺ → Mo⁴⁺ → Mo⁰) with Mo⁵⁺ and Mo⁴⁺. XRD analysis confirmed the formation of Mo₄O₁₁ phase as an intermediate phase followed by MoO₂ phase. After 60 min of isothermal reduction, peaks of metallic molybdenum (Mo) appeared. Whereas, FESEM analysis showed porous crater-like structure on the surface cracks of MoO₂ layer which led to the growth of Mo phase. Meanwhile, the reduction of MoO₃ catalyst in 10% carbon monoxide (CO) showed the formation of unstable intermediate phase of Mo₉O₂₆ at the early stage of reduction. Furthermore, by increasing 20% CO led to the carburization of MoO₂ phase, resulted in the formation of Mo₂C rather than the formation of metallic Mo, as confirmed by XPS analysis. Therefore, the presented study shows that hydrogen gave better reducibility due to smaller molecular size, which contributed to high diffusion rate and achieved deeper penetration into the MoO₃ catalyst compared to carbon monoxide reductant. Hence, the reduction of MoO₃ in carbon monoxide atmosphere promoted the formation of Mo₂C which was in agreement with the thermodynamic assessment.     

A distributed energy system integrating SOFC-MGT with mid-and-low temperature solar thermochemical hydrogen fuel production

Solar thermochemical hydrogen production with energy level upgraded from solar thermal to chemical energy shows great potential. By integrating mid-and-low temperature solar thermochemistry and solid oxide fuel cells, in this paper, a new distributed energy system combining power, cooling, and heating is proposed and analyzed from thermodynamic, energy and exergy viewpoints. Different from the high temperature solar thermochemistry (above 1073.15 K), the mid-and-low temperature solar thermochemistry utilizes concentrated solar thermal (473.15–573.15 K) to drive methanol decomposition reaction, reducing irreversible heat collection loss. The produced hydrogen-rich fuel is converted into power through solid oxide fuel cells and micro gas turbines successively, realizing the cascaded utilization of fuel and solar energy. Numerical simulation is conducted to investigate the system thermodynamic performances under design and off-design conditions. Promising results reveal that solar-to-hydrogen and net solar-to-electricity efficiencies reach 66.26% and 40.93%, respectively. With the solar thermochemical conversion and hydrogen-rich fuel cascade utilization, the system exergy and overall energy efficiencies reach 59.76% and 80.74%, respectively. This research may provide a pathway for efficient hydrogen-rich fuel production and power generation.     

Transesterification of Palm-based Methyl Palmitate into Esteramine Catalyzed by Calcium Oxide Catalyst

The technology for transesterification reactions between methyl esters and alcohols is well established by using classical homogeneous alkaline catalysts, which provide high conversion of methyl esters to specialty or nonindigenous esters. However, in certain products where the purity of the esters is of concern, the removal of homogeneous catalysts after the completion of the reaction is a challenge in terms of production cost and water footprint. Therefore, a study to investigate the potential of heterogeneous catalysts was conducted on reactions between methyl palmitate and triethanolamine. The degree of basicity and active surface area of calcium oxide (CaO), zinc oxide (ZnO), and magnesium oxide (MgO) were first characterized by using temperature-programmed desorption (TPD-CO₂) and Brunauere–Emmett–Teller (BET), respectively. Among the metal oxides investigated, the CaO catalyst showed the best catalytic activity toward the transesterification process as it gave the highest conversion of methyl palmitate and yielded fatty esteramine compositions similar to the conventional homogeneous catalyst. The optimum transesterification condition by using the CaO catalyst utilized a lower vacuum system of approximately 200 mbar, which could minimize a considerable amount of energy consumption. Furthermore, low CaO dosage of 0.1% was able to give a conversion of 94.5% methyl ester and formed esteramine at 170 °C for 2 h. Therefore, the production of esterquats from esteramine may become more economically feasible through the methyl ester route by using the CaO catalyst, which can be recycled three times.     

On‐the‐Spot Immobilization of Quantum Dots,Graphene Oxide,and Proteins via Hydrophobins

Class I hydrophobin Vmh2, a peculiar surface active and versatile fungal protein, is known to self‐assemble into chemically stable amphiphilic films, to be able to change wettability of surfaces, and to strongly adsorb other proteins. Herein, a fast, highly homogeneous and efficient glass functionalization by spontaneous self‐assembling of Vmh2 at liquid–solid interfaces is achieved (in 2 min). The Vmh2‐coated glass slides are proven to immobilize not only proteins but also nanomaterials such as graphene oxide (GO) and quantum dots (QDs). As models, bovine serum albumin labeled with Alexa 555 fluorophore, anti‐immunoglobulin G antibodies, and cadmium telluride QDs are patterned in a microarray fashion in order to demonstrate functionality, reproducibility, and versatility of the proposed substrate. Additionally, a GO layer is effectively and homogeneously self‐assembled onto the studied functionalized surface. This approach offers a quick and simple alternative to immobilize nanomaterials and proteins, which is appealing for new bioanalytical and nanobioenabled applications.     

Tungsten(VI) oxide supported rhodium nanoparticles: Highly active catalysts in hydrogen generation from ammonia borane

Herein, we report the use of tungsten(VI) oxide (WO₃) as support for Rh⁰ nanoparticles. The resulting Rh⁰/WO₃ nanoparticles are highly active and stable catalysts in H₂ generation from the hydrolysis of ammonia borane (AB). We present the results of our investigation on the particle size distribution, catalytic activity and stability of Rh⁰/WO₃ catalysts with 0.5%, 1.0%, 2.0% wt. Rh loadings in the hydrolysis reaction. The results reveal that Rh⁰/WO₃ (0.5% wt. Rh) is very promising catalyst providing a turnover frequency of 749 min^?1 in releasing 3.0 equivalent H₂ per mole of AB from the hydrolysis at 25.0 °C. The high catalytic activity of Rh⁰/WO₃ catalyst is attributed to the reducible nature of support. The report covers the results of kinetics study as well as comparative investigation of activity, recyclability, and reusability of colloidal(0) nanoparticles and Rh⁰/WO₃ (0.5 % wt. Rh) catalyst in the hydrolysis reaction.     

Single chamber Solid Oxide Fuel Cells selective electrodes: A real chance with brownmillerite-based nanocomposites

In this contribution brownmillerite-based nanocomposite cathode for Single-Chamber Solid Oxide Fuel Cells is developed. These cells can be very attractive especially for small and cheap devices because of the absence of seals. The efficiency of SC-SOFCs is strictly connected to the selectivity of anode and cathode, the bottleneck for this technology. The development of a cathode inert in fuel oxidation is particularly challenging. Our strategy is to start from a catalytically un-active support (CFA = Ca₂FeAl_0.95Mg_0.05O₅) and induce the formation of iron oxide based nanoparticles, expected to activate oxygen. Symmetric (CFA + FeO_x/CGO/CFA + FeO_x) and complete cells (CFA + FeO_x/CGO/Ni-CGO) are studied in air and methane/oxygen 2:1 mixture. The Area Specific Resistance of CFA + FeO_x is less than 1/3 that of CFA. The high selectivity allows to reach an efficiency of 25%; power still needs to be increased but we demonstrated the possibility to develop selective low cost electrodes. The effect of air, methane/oxygen exposure and the heat treatments were carefully investigated.     

Colloidal Synthesis of Hollow Cobalt Sulfide Nanocrystals

Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at > 120 °C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature‐dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell‐size statistics and transmission electron microscopy images of as‐grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system.     

含锌离子的聚硅硫酸铝的合成及性能研究

采用一步法制备聚硅硫酸铝絮凝剂合成了含锌离子的聚硅硫酸铝并研究了其性能.含锌离子絮凝剂是一种无毒高效的絮凝剂,且絮凝效果优良,锌离子含量对絮凝剂性能影响很大.