Structural and hydrogenation studies of ZnO and Mg doped ZnO nanowires

In this work, Mg doped zinc oxide (Mg_xZn_1−xO, x = 5, 10 and 20 at. %) nanowires were successfully prepared by two step process. Initially, ZnO nanowires were grown by thermal evaporation of Zn powder under oxygen atmosphere. Mg powder was doped in as grown ZnO through solid state diffusion at low temperature. Energy dispersive x-ray spectroscopy (EDAX), transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV–Visible absorption spectra analysis reveals that the Mg doping on ZnO nanowires induces lattice strain in ZnO. Rietveld analysis of XRD data confirms the wurtzite structure and a continuous compaction of the lattice (in particular, the c-axis parameter) as x increases. The hydrogenation properties of ZnO nanowires and Mg doped ZnO (Mg_xZn_1−xO, x = 0, 5, 10 and 20 at. %) nanowires were studied. The hydrogenated samples were further investigated through XRD and Fourier transform infrared spectroscopy (FTIR). The hydrogen storage capacity of as grown ZnO nanowires has been estimated to be 0.57 wt. % H₂ at room temperature. However, the hydrogen storage capacity gets increased to ∼1 wt. % upon doping ZnO with 10 at. % Mg. Further increase in Mg concentration decreases the hydrogen storage capacity of ZnO nanowires. Thus for 20 at. % Mg doped ZnO; the hydrogen absorption capacity gets decreased from ∼1 wt. % to 0.74 wt. %. The mechanism of hydrogen storage in ZnO nanowires and Mg doped samples of ZnO has been discussed.     

Characterization and the hydrogen storage capacity of titania-coated electrospun boron nitride nanofibers

In the present work, titania-coated (TiO₂) boron nitride nanofibers were produced by the electrospinning method, and the effect of heat treatment on the nanofibers was studied. Electrospinning method is often adopted for the synthesis of one-dimensional nanofibers due to high productivity, simplicity, and cost-effectiveness. In this study, boric oxide was deposited on co-electrospun polyacrylonitrile and TiO₂. TiO₂-coated boron nitride nanofibers, with a diameter of 100 nm, were obtained after heat treatment and nitridation. The effects of heat treatment on the morphology, surface area and hydrogen storage capacity were studied extensively. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) showed long, bead-free nanofibers and the presence of TiO₂ nanoparticles on the nanofibers. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy depicted hexagonal structures of boron nitride. The hydrogen uptake capacities of the nanofibers were investigated by pressure composition isotherm (PCI) in the pressure range of 1–70 bar at room temperature.     

Effect of in-situ boron doping on hydrogen adsorption properties of carbon nanotubes

Floating catalyst chemical vapor deposition method was used for the synthesis of boron doped carbon nanotubes (BCNTs) using ethanol, triethyl borate and ferrocene as carbon source, boron source and catalyst precursor, respectively. The synthesized BCNTs were characterized by transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy (XPS). The hydrogen adsorption activity was studied for BCNTs along with undoped single walled and multi walled carbon nanotubes. Significant enhancement in the hydrogen storage value was found in doped CNTs as compared to the other undoped CNTs. Hydrogen storage for BCNTs was found to be 2.5 wt% at 10 bar and 77 K. In-situ doped BCNTs gives higher hydrogen adsorption as compared to ex-situ doped BCNTs. The Langmuir adsorption isotherm was found to be suitable for describing the adsorption isotherm as compared with Freundlich isotherm. Maximum adsorption capacity was about 9.8 wt% at 77 K. Pseudo second order kinetics was followed by BCNTs for hydrogen adsorption.     

Study on the hydrogen storage properties of the dual active metals Ni and Al doped graphene composites

The graphene nanosheets are synthesized by modified Hummer's method, based on which the dual active metals Ni and Al doped graphene composites are prepared through in-suit reaction and self-assembly with high-temperature reduction process. The molecular structure, morphology and specific surface area of graphene nanosheets are characterized systematically. The phase composition, surface morphology and hydrogen storage properties of dual active metals Ni and Al doped graphene composites are further investigated by X-ray diffraction, scanning electron microscopy and gas reaction controller. Results show that the graphene nanosheets have typical graphene feature, whose transparent graphene edges can be observed clearly, and the specific surface area is as high as 604.2 m² g⁻¹. The Ni and Al doped graphene composites are composed with Ni, Al and C phases, which have high hydrogen storage capacity and excellent hydriding/dehydriding stabilities. The maximum hydrogen storage uptake of such composites is up to 5.7 wt% at 473 K, and the dehydriding efficiency is high as 96%∼97% at the dehydriding temperature of 380 K. The hydrogen adsorption and desorption rate control step of the Ni and Al doped graphene composites is complied to the nucleation and two-dimensional growth mechanism.     

Effect of platinum doping of activated carbon on hydrogen storage behaviors of metal-organic frameworks-5

In this work, we prepared platinum doped on activated carbons/metal-organic frameworks-5 hybrid composites (Pt-ACs-MOF-5) to obtain a high hydrogen storage capacity. The surface functional groups and surface charges were confirmed by Fourier transfer infrared spectroscopy (FT-IR) and zeta-potential measurement, respectively. The microstructures were characterized by X-ray diffraction (XRD). The sizes and morphological structures were also evaluated using a scanning electron microscopy (SEM). The pore structure and specific surface area were analyzed by N₂/77 K adsorption/desorption isotherms. The hydrogen storage capacity was studied by BEL-HP at 298 K and 100 bar. The results revealed that the hydrogen storage capacity of the Pt-ACs-MOF-5 was 2.3 wt.% at 298 K and 100 bar, which is remarkably enhanced by a factor of above five times and above three times compared with raw ACs and MOF-5, respectively. In conclusion, it was confirmed that Pt particles played a major role in improving the hydrogen storage capacity; MOF-5 would be a significantly encouraging material for a hydrogen storage medium as a receptor.     

Preheated self-aligned graphene oxide for enhanced room temperature hydrogen storage

This study explored the hydrogen adsorption capacity of self-assembled aligned graphene oxide at room temperature. The characteristics of as-prepared graphene oxide were determined by scanning electron microscopy, Raman spectroscopy, and X-ray diffractometry techniques. Three different temperatures were taken for preheating, i.e., 25, 250, and 400 °C. The maximum adsorption pressure was given to 20 bar, and we evaluated the hydrogen adsorption competency at room temperature (25 ± 2 °C). The maximum hydrogen storage capacity was achieved ~2.5 wt%, which was found for the graphene oxide sample preheated at 400 °C. This hydrogen storage capacity was 67% and 40% more than the graphene oxide samples preheated at 25 and 250 °C, respectively. Such an enhancement of hydrogen storage capacity in the self-aligned graphene oxide samples at room temperature is attributed to reduced interlayer spacing and increased topological defects in preheated graphene oxide samples at 400 °C.     

Assessment of the effect of electrophoretic deposition parameters on hydrogen storage performance of graphene oxide layer applied on nickel foam

In this study, the hydrogen storage capacity of the graphene oxide layer was studied electrochemically. The graphene oxide was synthesized by modified Hummers' method and applied on the nickel foam by electrophoretic deposition (EPD) method at different potentials (20 and 60 V) and times (20 and 60 min) to determine the effect of applied potential and time of deposition on the hydrogen adsorption performance. The hydrogen adsorption tests including charge-discharge test, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were conducted in 6 M KOH solution and at room temperature. Based on the achieved CV curves, the graphene oxide (GO) layer achieved at 60 V within 20 min has a higher electrochemical hydrogen adsorption capability compared to other obtained samples. The calculated hydrogen storage capacity is obtained 50.9 mA. h. g^?1. The rosette flower like morphology of the obtained GO layers at optimum condition, has an impressive effect on the improving electrochemical hydrogen adsorption based on morphology study by field emission scanning electron microscopy.     

Fabrication of zinc‐loaded hollow glass microspheres (HGMs) for hydrogen storage

The greatest challenge for a feasible hydrogen economy lies on the production of pure hydrogen and the materials for its storage with controlled release at ambient conditions. Hydrogen with its great abundance, high energy density and clean exhaust is a promising candidate to meet the current global challenges of fossil fuel depletion and green house gases emissions. Extensive research on hollow glass microspheres (HGMs) for hydrogen storage is being carried out world‐wide, but the right material for hydrogen storage is yet underway. But many other characteristics, such as the poor thermal conductivity etc. of the HGMs, restrict the hydrogen storage capacity. In this work, we have attempted to increase the thermal conductivity of HGMs by ZnO doping. The HGMs with Zn weight percentage from 0 to 10 were prepared by flame spheroidization of amber‐colored glass powder impregnated with the required amount of zinc acetate. The prepared HGMs samples were characterized using field emission‐scanning electron microscope (FE‐SEM), environmental SEM (ESEM), high‐resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy and X‐ray diffraction (XRD) techniques. The deposition of ZnO on the microsphere walls was observed using FE‐SEM, ESEM and HRTEM which was further confirmed using the XRD and ultraviolet–visible absorption data. The hydrogen storage studies done on these samples at 200 °C and 10‐bar pressure for 5 h showed that the hydrogen storage increased when the Zn percentage in the sample increased from 0 to 2%. The percentage of zinc beyond 2, in the microspheres, showed a decline in the hydrogen storage capacity. The closure of the nanopores due to the ZnO nanocrystal deposition on the microsphere surface reduced the hydrogen storage capacity. The hydrogen storage capacity of HAZn2 was found 3.26 wt% for 10‐bar pressure at 200 °C. Copyright © 2015 John Wiley & Sons, Ltd.     

Improved hydrogen adsorption of ZnO doped multi-walled carbon nanotubes

Hydrogen storage is still one of the most important problems to improve hydrogen energy usage widespread. New materials capable of storing hydrogen with high efficiency must be introduced to overcome this problem. In recent years, addition of metals or inorganic compounds to multiwalled carbon nanotubes (MWCNTs) has been generally used for hydrogen uptake studies to enhance adsorption property of the nanotubes. In this study, Zinc oxide (ZnO) nanoparticles doped MWCNTs (ZnO-MWCNTs) have been produced as new reversible hydrogen storage materials, and we have investigated characterization of ZnO-MWCNTs by XRD, SEM, TGA, TEM and BET analyses. The functionalized MWCNTs and ZnO doped MWCNTs were subjected to hydrogenation step by dynamic gas sorption analyser under pressure of 5–50 bar. The hydrogen uptake capacities of the materials under different pressures were measured gravimetrically. It was indicated that by controlling the pressures for hydrogenation of ZnO-MWCNTs induces the spillover of ZnO nanoparticles in the layer of MWCNTs which in return with high hydrogen adsorption capacity. Consequently, the hydrogen adsorption of the functionalized MWCNTs (f-MWCNTs) and the ZnO-MWCNTs were achieved to be 1.05 wt% and 2.7091 wt% under pressure of 50 bar as maximum.     

Preparations of different ZnO nanostructures on TiO2 nanotube via electrochemical method and its application in hydrogen production

In the present study, zinc oxide doped titanium dioxide nanotubes (ZnO/TiO₂-NTs) were designed by using electrochemical deposition method. Titanium dioxide nanotubes (TiO₂-NTs) were fabricated by anodization method. Nanostructured ZnO was deposited with various deposition times on TiO₂-NTs. The morphological, structural, optoelectronic properties of ZnO/TiO₂-NTs were examined in detail. The morphological and structural characterization of obtained electrodes was investigated with help of field emission scanning electron microscopy and X-ray diffraction. ZnO nanostructures with three different morphologies were obtained from nanotowers to nanoleafs. XRD results depicted that ZnO nanostructures have the high crystallinity with hexagonal wurtzite structure. The measurements of the contact angle were utilized to determine the wetting behavior of the obtained surface of materials. Electrochemical impedance spectroscopy measurement was used in 1 M KOH to investigate electrocatalytic behavior of the obtained materials towards hydrogen evolution reaction. Flat band potentials, as well as charge carrier densities, were determined by using Mott-Schottky analysis. The charge carrier densities were calculated as 1.06 × 10¹⁹ and 1.66 × 10²⁰ cm⁻³ for TiO₂-NTs and 30-ZnO/TiO₂-NTs, respectively. The energy consumption and energy efficiency were determined for hydrogen evolution on ZnO/TiO₂-NTs electrodes.     

Synthesis and characterization of ZnO nanowires grown on different seed layers: The application for dye-sensitized solar cells

Zinc oxide (ZnO) nanowire electrodes which were grown on different seed layers and examination of their significant effects on the performance of dye sensitized solar cells were studied. Through chemical bath deposition process, the ZnO nanowires were grown on an indium tin oxide (ITO) coated glass using sputter-deposited aluminum doped zinc oxide (AZO) and ZnO seed layers. Afterward, main parameters such as solution concentration, growth temperature, and time were systematically investigated based on morphology of nanowires. The X-ray diffraction (XRD), field emission scanning microscopy (FESEM), and photoluminescence (PL) were applied to investigate the characteristics of the samples. The results showed ZnO nanowires, which were grown by AZO seed layer, had a high density array with hexagonal wurtzite structure distributed vertically and uniformly on ITO coated glass. The mentioned zinc-oxide nanowires grown under an optimum condition on different seed layer were used to fabricate dye solar cells afterward. The seed layer was effective on morphologic, optical, and structural features. The overall light-conversion efficiency of dye sensitized solar cell with ZnO nanowires grown on AZO seed layer was almost 2 times higher than that of those grown on ZnO seed layer. Electrochemical impedance spectroscopy analysis was measured under standard light to investigate the electron transport properties in the both ZnO-NW DSSCs. As the results showed, photoanode electron recombination rate with electrolyte was 6.02 Hz for dye solar cells of zinc oxide (ZnO-NWDSSC) produced by ZnO seed layer, which is 2.5 times faster than cells with AZO seed layer.     

Agent-free synthesis of graphene oxide/transition metal oxide composites and its application for hydrogen storage

Graphene oxide (GO) wrapped transition metal oxide composite materials were synthesized by a very simple route without any additional agents and the hydrogen adsorption properties of the materials were investigated. The morphologies of GO/V₂O₅ and GO/TiO₂ were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that single- or few-layered GO sheets wrapped throughout the V₂O₅ and TiO₂ particles. According to X-ray photoelectron spectroscopy (XPS), the C–OH species of GO and the surface-adsorbed oxygen of the transition metal oxide bond together via a dehydration reaction. The wrapping phenomenon of GO causes the enhancement of hydrogen storage capacity at liquid nitrogen temperature (77 K) compared with those of the pristine transition metal oxides and GO. The enhancement of hydrogen storage capacity of GO-wrapped transition metal oxide composite materials results from the existence of interspaces between the transition metal oxide particles and the thin GO layers.     

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.     

Hybrid hollow structures for hydrogen storage

Nanohybrids have shown considerable promise for hydrogen storage due to their enhanced capacity and fast kinetics. Hollow nanostructures have attracted considerable attention in diverse contexts and recently have been envisaged as nanocontainers for hydrogen storage. In the current work a two-scale novel hollow nanohybrid is synthesized, wherein the outer Ni ‘capsule’ plays a catalytic role in the breakdown of hydrogen molecule into atomic form and the inner Mg hollow structure enhances the hydrogen storage via a multi-mode storage philosophy developed recently. The structure of the dual-phase nanohybrid is elucidated using transmission electron microscopy and selected area diffraction patterns and characterized for hydrogen storage via pressure-composition-isotherms. The system shows good hydrogen storage capacity (∼5 wt% at 10 bar & 180 °C); coupled with fast kinetics. The hydrogen is stored in an additional form than that reported earlier (interstitial compound).     

Microstructural evolution during low temperature sorption cycling of Mg-AlTi multilayer nanocomposites

We studied the hydrogen storage behavior of sputtered Mg-AlTi multilayers where nanometric Mg or Mg–Al–Ti layers were confined by 2 nm thick layers of AlTi. By decreasing the thickness of Mg layers, we were able to achieve 5.1 wt.% H capacity without significant degradation in over 200 cycles at 473 K. However, for the samples with pure Mg layers degradation eventually occurred at higher cycle numbers. In multilayers of 34 nm thick Mg degradation was followed by disintegration of the films into sponge-like flakes. Alloying Mg layers with Al and Ti through cosputtering improved the performance of the multilayer composites. Through cycling, Al and Ti segregated out of Mg matrix and formed a nanocrystalline/amorphous AlTi phase as observed by X-ray diffraction and electron microscopy. This improved resistance of the microstructure against coarsening while a well dispersion of AlTi particles was achieved. Moreover, the stability of multilayers enhanced to an extent that they not only preserved their physical integrity, also did they maintain their superior kinetics up to over 250 cycles. Pressure - composition isotherms showed no significance change in thermodynamics of MgH₂ formation.     

A new catalyst of AlCu@ZnO for hydrogen evolution reaction

Thin films of undoped ZnO, Al-doped ZnO, Cu-doped ZnO, and AlCu@ZnO deposited on indium tin oxide were performed by the sol-gel spin coating method. The prepared ZnO thin films were investigated for their structural and electrical properties after annealing at 500 °C for 1 h. ZnO thin films were characterized by electrochemical impedance spectroscopy, linear sweep voltammetry, scanning electron microscopy, Fourier transform infrared spectroscopy and Mott Schottky. According to the results obtained from the Nyquist diagrams of the ZnO thin films, the resistance value was found to decrease with binary doping and the resistance value was found to be lowest in AlCu@ZnO doped thin film containing 0.01 M Al and 0.1 M Cu. As ZnO thin films go to cathodic potentials, it is seen that the cathodic current value of ZnO with undoped is the lowest. It has been found that only Al and Cu doping showed less cathodic current than double doping.     

Synthesis of boron and nitrogen co-doped carbon nanotubes and their application in hydrogen storage

Boron and nitrogen codoped carbon nanotubes (B,N-CNTs) were synthesized by floating catalyst chemical vapor deposition (FCCVD) using ethanol, ferrocene, boric acid and imidazole as carbon source, catalyst, boron and nitrogen precursors, respectively. The samples were analyzed using transmission electron microscopy, Raman spectroscopy, thermogravimetric analysis and X-ray photoemission spectroscopy. 1.5 at% B and 1.34 at% N could be doped in the resultant structure, which has higher length (few μm) with higher thermal stability (621 °C). At pressure 16 bar, hydrogen adsorption for B,N-CNTs was found to be 1.96 and 0.35 wt% at 77 K and 303 K, respectively. Hydrogen storage as function of time was also reported for both the cases. The adsorption process follow pseudo second order kinetics. The present study reveals that the codoping of CNTs aid in tuning properties of CNTs for hydrogen storage application.     

Bio-hydrogen production based on catalytic reforming of volatiles generated by cellulose pyrolysis: An integrated process for ZnO reduction and zinc nanostructures fabrication

The paper presents a process of cellulose thermal degradation with bio-hydrogen generation and zinc nanostructures synthesis. Production of zinc nanowires and zinc nanoflowers was performed by a novel processes based on cellulose pyrolysis, volatiles reforming and direct reduction of ZnO. The bio-hydrogen generated in situ promoted the ZnO reduction with Zn nanostructures formation by vapor-solid (VS) route. The cellulose and cellulose/ZnO samples were characterized by thermal analyses (TG/DTG/DTA) and the gases evolved were analyzed by FTIR spectroscopy (TG/FTIR). The hydrogen was detected by TPR (Temperature Programmed Reaction) tests. The results showed that in the presence of ZnO the cellulose thermal degradation produced larger amounts of H₂ when compared to pure cellulose. The process was also carried out in a tubular furnace with N₂ atmosphere, at temperatures up to 900 °C, and different heating rates. The nanostructures growth was catalyst-free, without pressure reduction, at temperatures lower than those required in the carbothermal reduction of ZnO with fossil carbon. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The optical properties were investigated by photoluminescence (PL). One mechanism was presented in an attempt to explain the synthesis of zinc nanostructures that are crystalline, were obtained without significant re-oxidation and whose morphologies are dependent on the heating rates of the process. This route presents a potential use as an industrial process taking into account the simple operational conditions, the low costs of cellulose and the importance of bio-hydrogen and nanostructured zinc.     

Hydrogen storage in boron-doped carbon nanotubes: Effect of dopant concentration

Boron-doped carbon nanotubes (BCNTs) with varying B content (0–8 at%) were prepared by thermo-catalytic decomposition of ethanol in presence of boric acid at 1073 K. It was observed that hydrogen adsorption capacity improved to a critical B content of 3.86 at% and then decreased. Maximum hydrogen adsorption was found to be 0.497 wt% at 273 K and 16 bar with 3.86 at% of boron doping in CNTs. With the help of transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy, it was found that in addition to dopant concentration, dopant bonding with carbon structures, crystallinity and defects play pivotal roles in determining the extent of hydrogen adsorption by BCNTs. The thermogravimetric studies revealed the oxidation stability of the BCNTs. The hydrogen adsorption kinetics was found to follow the pseudo-second-order model. The rate constant value was minimum for the BCNT with the highest hydrogen storage capacity.     

Synthesis and hydrogen storage properties of ultrafine Mg-Zn particles

Mg-6.9 at.% Zn ultrafine particles (UFPs) were prepared by hydrogen plasma-metal reaction (HPMR) method. The electron microscopy study revealed that they were spherical in shape with particle size in the range 100-700 nm. Each fine particle was composed of single crystal structure of α-Mg(Zn) solid solution and amorphous structure of Mg-Zn alloy. After one absorption and desorption cycle, these UFPs transformed from the single crystal into the nanocrystalline structure and the mean particle size changed from 400 to 250 nm. It was found that the Mg-Zn UFPs could absorb 5.0 wt.% hydrogen in 20 min at 573 K and accomplish a high hydrogen storage capacity of 6.1 wt.% at 573 K. The fine particle size, nanocrystalline structure and the low oxide content of the obtained sample promoted the hydrogen sorption process with low hydrogen absorption activation energy of 56.3 kJ/mol. The enhanced hydrogen sorption properties of high absorbing rate and high storage capacity were due to the improved kinetics rather than the change in enthalpy.