Porous silicon bandgap broadening at natural oxidation

Emission and excitation photoluminescence spectra of porous silicon thin layers have been investigated at natural oxidation. The shift of both types of spectra to high-energy region with time has been shown. Analysis of excitation spectra points out the indirect behavior of electron transitions responsible for visible photoluminescence, which remains unaltered at natural oxidation. The value of optical bandgap is estimated in each case. It is shown that the optical bandgap broadens during oxidation due to size reduction of silicon nanocrystallites.     

On the use of the digital image correlation method for heterogeneous deformation measurement of porous solids

In this paper, several crucial issues arising from the application of the digital image correlation (DIC) method to the measurement of heterogeneous deformation of porous solids are discussed. To handle samples with complex geometry, the performance of the two commonly employed DIC methods, namely the subset-based DIC and the finite-element based DIC methods are first evaluated and compared. A combined DIC approach and an adaptive DIC approach suitable for samples with discontinuities/holes are then proposed. Aluminum plates with circular holes subject to compressive loading are employed to evaluate the accuracy of the proposed methods. It has been found that in addition to other factors such as the number of pixels and speckle size, the orientation of the camera lens also plays an important role on the measurement accuracy. A calibration method for the adjustment of camera orientation is proposed, which leads to a good agreement between the experimentally measured displacements and finite element simulation results. Another finding of the presented work is that for relatively stiff specimens, the deformation of the loading system itself must be considered in order to obtain an accurate displacement.     

A green synthetic approach to graphene nanosheets for hydrogen adsorption

A green and facile strategy of preparing graphene by reducing exfoliated graphite oxide (GO) with glucose was developed in this study. The as-prepared samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Atomic force microscopy (AFM). The characterization results indicated that the graphene sheets (GS) were of high quality with smooth surface, rich pore structure and few layer graphene. The samples have a BET specific surface area of 1205.8 m² g⁻¹ measured by N₂ adsorption at 77 K. The hydrogen storage capacity of 2.7 wt.% at 298 K and 25 bar demonstrated that the as-prepared graphene employing glucose as reductant is supposed to be a promising material with outstanding property for hydrogen storage.     

Morphological and optical properties changes in nanocrystalline Si (nc-Si) deposited on porous aluminum nanostructures by plasma enhanced chemical vapor deposition for Solar energy applications

Photoluminescence (PL) spectroscopy was used to determine the electrical band gap of nanocrystalline silicon (nc-Si) deposited by plasma enhancement chemical vapor deposition (PECVD) on porous alumina structure by fitting the experimental spectra using a model based on the quantum confinement of electrons in Si nanocrystallites having spherical and cylindrical forms. This model permits to correlate the PL spectra to the microstructure of the porous aluminum silicon layer (PASL) structure. The microstructure of aluminum surface layer and nc-Si films was systematically studied by atomic force microscopy (AFM), transmission electron microscopy (TEM), Raman spectroscopy and X-ray diffraction (XRD). It was found that the structure of the nanocrystalline silicon layer (NSL) is dependent of the porosity (void) of the porous alumina layer (PAL) substrate. This structure was performed in two steps, namely the PAL substrate was prepared using sulfuric acid solution attack on an Al foil and then the silicon was deposited by plasma enhanced chemical vapor deposition (PECVD) on it. The optical constants (n and k as a function of wavelength) of the deposited films were obtained using variable angle spectroscopic ellipsometry (SE) in the UV-vis-NIR regions. The SE spectrum of the porous aluminum silicon layer (PASL) was modeled as a mixture of void, crystalline silicon and aluminum using the Cauchy model approximation. The specific surface area (SSA) was estimated and was found to decrease linearly when porosity increases. Based on this full characterization, it is demonstrated that the optical characteristics of the films are directly correlated to their micro-structural properties.     

One-step, template-free route to silver porous hollow spheres and their optical property

Silver porous hollow spheres (SPHS) were fabricated via ultrasonic spray pyrolysis of aqueous solutions containing AgNO₃ and glucose. In the hot spherical liquid droplets, glucose, as reducing agent, reacted with Ag⁺ to form Ag nanoparticles, which subsequently moved to the periphery of the hot liquid droplets to form Ag nanoparticles-glucose hybrid shell. With the temperature further increased, aforementioned Ag nanoparticles melted to form Ag skeleton decorated with unreacted glucose, which converted to SPHS via dissolving unreacted glucose in water. Due to their porous hollow structures, SPHS exhibited a wide Vis-NIR adsorption in the range of 400-1100 nm.     

Self-assembled MnS flower-like hierarchical architectures on porous alumina membrane

MnS flower-like hierarchical architectures were self-assembled on the surface of porous alumina membrane (PAM) under hydrothermal condition. The diameter of MnS flower-like hierarchical architectures is about 2-4 μm, which are composed of single-crystal nanowires with width of 70-80 nm. X-ray diffraction and high-resolution transmission electron microscopy analysis demonstrated the nanowire have preferred orientation along [1 1 0] direction. Prolonged reaction time would result in hollow spheres. Studies show that PAM and gas bubbles formed within the nanopores of PAM under hydrothermal condition play an important role in the formation process of MnS flower-like hierarchical architectures. The room-temperature PL spectrum shows a strong emission peak at 420 nm corresponding to the MnS band edge emission.     

A novel proton-exchange porous silicon membrane production method for μDMFCs

This study introduces a new production method to use as a porous silicon-based proton exchange membrane for μDMFCs. In this respect, EIS, fuel crossover test, and fuel cell performance test at the μDMFC sample cell are performed at room temperature on a porous silicon-based membrane that was produced for passive mode μDMFC as a proton exchange membrane. The reason for performing the fuel crossover test is to ensure the silicon opened pores along the silicon wafer and to examine the fuel permeability of the membrane. The fuel crossover test shows that the fuel cell provides energy for about 60 min with a 50 mL fuel. EIS reveals proton permeability of proton exchange membrane. The calculated value of the conductivity of the membrane is 0.0016 S/cm. OCV of the system is 0.4V, whereas values (with highest power density is 0.1 mW/cm²and with the highest current density is 0.39 mA/cm²) are low. However, porous silicon is not a natural proton conductor. Hence, these values can be increased by different ways such as porous silicon functionalized, or serial connection of fuel cells. On the other hand, the value of OCV is consistent with the previous studies. In sum, this study presents a simple, cost-effective, and short time-consuming method for the production of porous silicon as proton-conducting membrane behavior.     

Adsorption of organochlorine pesticides on modified porous Al30/bentonite: Kinetic and thermodynamic studies

Adsorption of pesticides (heptachlor epoxide, dieldrin and endrin) onto modified bentonite by Keggin cation [Al₃₀O₈(OH)₅₆(H₂O)₂₄]¹⁸⁺ denoted Al₃₀ cation to form composite (Al₃₀/B), has been investigated as a possible alternative method for their removal from aqueous solutions. The study was aimed to use a low-cost material as a step towards cleaner environment. Interestingly, these chemical modifications altered the physicochemical characteristics of bentonite in term of morphology, surface area and functionality which has been confirmed by using nitrogen adsorption–desorption isotherm, scanning electronic microscopy (SEM) and X-ray diffraction (XRD). Gas chromatography coupled to mass spectrometry (GC–MS) was used to identify and analyze the pesticides. Different physicochemical parameters were analyzed: contact time, adsorbent dose, pH, and temperature. The results showed that the removal percentage of pesticides on Al₃₀/B was the highest at contact time of 5 h, adsorbent dosage of 25 mg, at pH 7.5, and at optimum temperature of 45 °C. Furthermore, the Kinetic study indicated that the adsorption of pesticides on Al₃₀/B was well adapted to the pseudo-first order kinetic with a correlation coefficient near unity. The results of adsorption were fitted to the Langmuir and Freundlich isotherms. The Freundlich model represented the adsorption process better than Langmuir model, with correlation coefficients (R²) values range from 0.986 to 0.989. The Thermodynamic study suggested that the adsorption of pesticides was chemisorption, spontaneous and endothermic process. Therefore, Al₃₀/B composite can be utilized effectively for removal of pesticides with efficiency up to 98%.     

Influence of impregnation conditions on the activity of CrOx/Al2O3 catalysts in dehydrogenation of isobutane in fixed bed reactor

The development of catalysts for dehydrogenation of light paraffin hydrocarbons in a fixed bed reactor is of great importance for the world petrochemical industry. The preparation of granules (~3 mm in diameter) of CrO_x/Al₂O₃ catalysts is hindered by such problems as homogeneous distribution of active component and modifiers, high strength of granules, etc. In this paper, the alumina support dissolution in the impregnating solution containing chromic acid and the opportunity to apply vacuum impregnation to minimize this effect in the preparation of CrO_x/Al₂O₃ catalysts are discussed. A series of catalysts is synthesized at different impregnation pressures (1, 0.85, and 0.7 atm), characterized by a complex of physical–chemical methods (low-temperature N₂ adsorption, SEM, XRD, TPR-H₂), and tested in isobutane dehydrogenation. The use of vacuum impregnation is shown to lead to the reduction of the specific surface area of the catalysts from to 91 to 56 m²/g and the growth of content of CrO_x phases that decreases the catalytic activity in dehydrogenation. The isobutylene yield at 610 °C decreases from 68% to 54% for the catalyst prepared at P = 0.7 atm as compared with the one prepared at atmospheric pressure. The high activity and stability are connected with the hierarchical structure of the alumina support and homogeneous chromia distribution on its surface.     

Architected porous metals in electrochemical energy storage

Porous metallic structures are regularly used in electrochemical energy storage (EES) devices as supports, current collectors, or active electrode materials. Bulk metal porosification, dealloying, welding, or chemical synthesis routes involving crystal growth or self-assembly, for example, can sometimes provide limited control of porous length scale, ordering, periodicity, reproducibility, porosity, and surface area. Additive manufacturing has shown the potential to revolutionize the fabrication of architected metals, allowing complex geometries not usually possible by traditional methods, by enabling complete design freedom of a porous metal based on the required physical or chemical property to be exploited. We discuss properties of porous metal structures in EES devices and provide some opinions on how architected metals may alleviate issues with electrochemically active porous metal current collectors, and provide opportunities for optimum design based on electrochemical characteristics required by batteries, supercapacitors or other electrochemical devices.