A need was identified to test multi–layer vacuum super insulation (MLVSI) used in cryogenic applications for hydrogen storage. The study focuses on the application of commercially available MLVSI to a locally patented liquid hydrogen cryogenic storage system. This led to an investigation of different types of multi–layer vacuum insulation configurations, as well as further research on tank inlet coupling configurations. It includes the manufacturing of a liquid nitrogen testing cryostat to be able to test and evaluate the system performance. The first set of tests was based on the development of an inlet coupling configuration to limit heat transfer through the inner tank inlet, of a double cryogenic tank system in order to reduce gas boil–off. The couplings were manufactured in the form of a bellow to handle cryogenic vacuum levels, while ensuring low heat transfer rates between inner and outer tanks. It was found that various coupling designs can be considered to limit gas boil–off. The second set of tests was conducted on a specific MLVSI configuration to determine its effectiveness to insulate the spherical header surface of a typical hydrogen storage vessel. The installation procedure, to limit heat transfer and boil–off due to edge effects in this configuration was investigated. It was found that insulation–overlap–edge effects will always have an impact on insulation performance when a spherical header of a storage vessel is insulated, due to its specific geometry. A time efficient way to install MLVSI on such a spherical header is presented and evaluated. Further investigations were carried out by combining findings into one single system to determine the performance of an optimised insulated cryogenic system. It was found that copper plate discs installed between the vanes of a bellowed inlet/outlet nozzle is the most promising to limit heat transfer to the cryogenic fluid. / Thesis (M.Ing. (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2012.

Hydrogen diffusion is investigated in a 50 nm film of vanadium and a vanadium superlattice. Diffusion constants for three different temperature and pressure pairs are determined for the 50 nm film. The diffusion constants for the temperature and pressure pairs are determined to be 4.5 $\pm$ 0.1 $\cdot 10^{-5} \text{ cm}^{-2}$ at 463 K and 0.05 H/V, 5.6 $\pm$ 0.1 $\cdot 10^{-5} \text{ cm}^{-2}$ at 463 K and 0.12 H/V and 8.0 $\pm$ 0.2 $\cdot 10^{-5} \text{ cm}^{-2}$ at 493 K and 0.05 H/V. The temperature and concentration dependence of the diffusion constants are determined. A concentration dependence of the diffusion constant is found with a higher rate of diffusion for a higher hydrogen concentration. The activation energy of chemical diffusion is determined to be 0.38 $\pm$ 0.03 eV.

>Magister Scientiae - MSc / Transition metals are a group of metals which are light in weight and have high hydrogen solubility. Their interaction with hydrogen is exorthermic and this phenomenon makes them “ideal” candidates for various applications of hydrogen storage systems. This explains why the phenomenon of hydrogen storage in Pd is used as a model for hydrogen storage systems because of the nature of absorption associated with it (like a sponge even at low temperatures). The hydrogenation process can be conducted at either room or high temperatures in a furnace under low pressure-low hydrogen gas concentration-short hydrogenation time (LP-LC-ST) and in intelligent gravimetric analyser under high pressurehigh hydrogen gas concentration-long hydrogenation time conditions. Most of the research on hydrogen storage sytems is based on gravimetric analysis of absorbed and desorbed hydrogen concentration. In this work, a comparison study of the hydrogen content in pure Pd, Pd-Pt coated systems, Pd-Pt alloys, commercially pure Ti and Ti-6Al-4V alloy determined by gravimetric methods and elastic recoil detection analysis (which is based on the detection of recoiled hydrogen after interaction with He+ ions) technique was investigated. The changes in the structural properties and the hydrogen content of the materials when exposed to a hydrogen gas environment for different durations at various system temperatures and pressures will be reported. These changes have an effect on the microstructure of CP-Ti and Ti-6Al-4V alloy and structural properties of all the hydrogenated materials. The results obtained from optical microscopy, scanning electron microscopy, x-ray diffraction, intelligent gravimetric analyser, digital balance, elastic recoil detection analysis and Vickers hardness test, show the following: it is found that hydrogenation of Pd at elevated temperatures (550 ˚C and 650 ˚C) does not yield hydrides under LP-LC-ST conditions. However, at room temperature the absorption of hydrogen occurred faster at the beginning of the process. Furthermore, the absorption of hydrogen increased with pressure where optimum absorption (0.67 wt. % hydrogen concentration) occurred under a system pressure of 2000 mbar. After pressure release, the remaining hydrogen content in the Pd sample was 0.6 wt. %. The Pd-Pt coated system provide hydrogen mobility at 550 and 650 ˚C where hydrides were formed under LP-LC-ST conditions. In addition to the decrease of hydrogen solubility in Pd-Pt alloys with an increase in Pt content, the probability of the alloys to achieve full saturation also decreases with an increase in Pt content under HP-HC-LT conditions. CP-Ti and Ti-6Al-4V alloy absorb substantial amount of hydrogen in the first hour of room temperature hydrogenation under LP-LC-ST conditions but hydrides were not formed. Therefore, under LP-LC-ST conditions at room temperature, Pd is able to store hydrogen in the form of hydrides whereas Ti and Ti-6Al-4V alloy could not. The 550 ˚C is the optimum temperature for hydrogenation of CP-Ti under LP-LC-ST conditions. The Ti- 6Al-4V alloy absorb optimum hydrogen at 650 ˚C under LP-LC-ST conditions. Consequently, the change of microhardness of CP-Ti and Ti-6Al-4V alloy was found to depend on hydrogenation temperature.

Carbon-based materials have attracted great attention over past few years in hydrogen storage applications. In particular, nanofibrous carbon working as support for sodium alanate exhibits great improvement in the kinetics of H2 releasing/uptaking. Herein, we used graphene with various dopants to simulate the carbon materials and performed a periodic density functional theory study on the impact of the modifications on the hydrogen interaction in the supported sodium alanate. Our results showed that the impact of various defects and dopants can be categorized in groups: (i) Pristine graphene and pentagon-heptagon (5-7) pair defective graphene, as well as nitrogen and sulfur doped graphene do not promote H2 formation. (ii) Carbon vacancies, as well as boron and chlorine doped systems, cause instantaneous H2 formation. (iii) Oxygen, phosphor and fluorine doped graphene led to the formation of a meta-stable di-hydrogen state with a H-H distance of ~ 0.96 Å. In addition, we confirmed the importance of van der Waals interaction in our system.

>Magister Scientiae - MSc / Due to the rapid depletion of fossil fuel reserves and the production of environmentally harmful by-products such as carbon dioxide, there is an urgent need for alternate sustainable clean energy. One of the leading candidates in this endeavour is hydrogen, which can be used as an energy carrier since it has a high energy density, zero emissions and is produced from non-depletable resources such as water. The major challenge hindering a hydrogen economy is the lack of safe and effective storage technologies for mobile applications. A prospective solution to this problem lies in the use of porous powdered materials, which adsorb the hydrogen gas. However, the integration of these powdered materials into a storage tank system, results in the pipelines being contaminated during filling cycles. This necessitates the shaping of the porous powdered materials. Among the many shaping techniques available, the electrospinning technique has been proposed as a promising technology since it is a versatile process that is easily scaled-up making it attractive for the applications of the study. Furthermore, the electrospinning process enables the synthesis of nano-sized fibres with attractive hydrogen sorption characteristics. In this regard, the current study employs the electrospinning technique to synthesise electrospun composite fibres for mobile hydrogen storage applications. After electrospinning three polymers, polyacrylonitrile (PAN) was selected as the most suitable polymer because it yielded bead-free electrospun fibres. However, the diameter of the PAN fibres was large/thick which prompted further optimisation of the electrospinning parameters. The optimised electrospinning conditions that yield unbeaded fibres within the desired diameter range (of 300-500 nm) were a PAN concentration of 10 wt%, a flow rate of 0.4 mL/h, a distance of 10 cm between the needle tip and collector plate, and an applied voltage of 8 kV. The study then progressed to the synthesis and characterisation of the pristine porous powdered materials which adsorb hydrogen gas. The porous powdered materials investigated were commercial zeolite 13X, its synthesised templated carbon derivative (ZTC) and Zr (UiO-66) and Cr (MIL-101) based metal-organic frameworks (MOFs). ZTC was synthesised via liquid impregnation coupled with chemical vapour deposition (CVD), and the MOFs were synthesised by the modulated solvothermal method. Analysis of the ZTCs morphology and phase crystallinity show that the carbon templated process using zeolites was successful, however, ZTC was amorphous compared to crystalline zeolite template. The BET surface area was assessed with the aid of nitrogen sorption isotherms for both zeolite 13X and ZTC, and values of 730 and 2717 m²/g, respectively were obtained. The hydrogen adsorption capacity for zeolite 13X was 1.6 wt% and increased to 2.4 wt% in the ZTC material at 77 K and 1 bar. The successful synthesis of well defined, crystalline MOFs was evident from X-ray diffraction and morphological analysis. The BET surface area and hydrogen adsorption for Zr MOF were 1186 m²/g and 1.5 wt%, respectively at 77 K and 1 bar. Cr MOF had a BET surface area of 2618 m²/g and hydrogen adsorption capacity of 1.9 wt% at 77 K and 1 bar. The main focus of the study was to synthesise electrospun composite fibres that can adsorb hydrogen gas and thus provide significant insight in this field of research. As such it examined composite fibres that incorporates porous powdered materials such as zeolite 13X, ZTCs, UiO-66 (Zr) MOF and MIL-101 (Cr) MOF and investigated their ability to adsorb hydrogen gas, which have not been reported previously. The synthesis of composite fibres was achieved by incorporating the porous powdered materials into the PAN resulting in a polymeric blend that was then electrospun. Morphological analysis illustrated that the porous powdered materials were successfully supported by or incorporated within the PAN fibres, forming composite fibres. The BET surface area of the 40 wt% zeolite-PAN and 12.5 wt% ZTC-PAN composite fibres were 440 and 1787 m²/g respectively. Zr MOF and Cr MOF composite fibres had a BET surface area of 815 and 1134 m²/g, respectively. The BET surface area had reduced by 40, 34, 31 and 57% for zeolite 13X, ZTC, Zr MOF and Cr MOF, respectively after these porous powdered materials were incorporated into PAN. The hydrogen adoption capacity for 40 wt% zeolite-PAN, 12.5 wt% ZTC-PAN, 20 wt% Zr MOFPAN and 20 wt% Cr MOF-PAN composite fibres was 0.8, 1.8, 0.9 and 1.1 wt%, respectively. This decrease was attributed to the limited amount of porous powdered materials that could be incorporated into the fibres since only 40 wt% of zeolite 13X, 12.5 wt% of ZTC and 20 wt% of the MOFs were loaded into their respective composite fibres. This was due to the fact that incorporation of greater amounts of porous powdered materials resulted in a viscous polymeric blend that was unable to be electrospun. It is evident from the study that electrospinning is a versatile process that is able to produce composite fibres with promising properties that can potentially advance the research in this field thus providing a practical solution to the problem of integrating loose powdered materials into an on-board hydrogen storage system. / CSIR Young Researchers Establishment Fund (YREF)

As the world is moving towards a more sustainable energy perspective, construction equipment sees the requirement to change its current way of operation with fossil fuels to reduce its environmental impact. In order to pursue the electrification of construction equipment a dense power source is essential, where hydrogen powered fuel cells have the potential to be a sufficient energy source. This thesis work is carried out in order to find the least CO2 emissive pathway for hydrogen to various construction sites. This is done by collecting state of the art data for production, processing and storage technologies. With the assembled data an optimization model was developed using mixed integer linear programming. The technologies found that showed promising adaptability for construction equipment in the state of art regarding production were steam methane reforming (SMR), proton exchange membrane electrolyser (PEMEC) and alkaline electrolyser. They showed promising characteristics due to their high level of maturity and possibility for reducing the environmental impact compared to the current operation. To investigate the hydrogen pathway and its possibilities, four scenarios were created for four types of construction sites. The scenarios have different settings for distance, grid connection and share of renewables, where the operations have various energy profiles that is to be satisfied. The optimal hydrogen pathway to reduce the CO2 emissions according to the model, were either PEMEC on-site or gaseous delivery of SMR CCS produced hydrogen. The share of renewables in the energy mix showed to be an important factor to determine which of the hydrogen pathways that were chosen for the different scenarios. Moreover, in the long run PEMEC was considered to be a more sustainable solution due to SMR using natural gas as feedstock. It was therefore concluded that for a high share of renewables PEMEC was the optimal solution, where for a low share of renewables SMR CCS produced hydrogen was optimal as the energy mix would result in a more emissive operation when using PEMEC.

Formic acid (FA) has been considered as one of the most promising materials for hydrogen storage today. The catalytic decarboxylation of formic acid ideally leads to the formation of CO2 and H2, and such CO2/H2 mixtures can be successfully applied in fuel cells. A large number of transition-metal based homogeneous catalysts with high activity and selectivity have been reported for the formic acid decarboxylation. In this presentation, we report ruthenium and rhodium complexes containing an N, N′-diimine ligand for the selective decomposition of formic acid to H2 and CO2 in water in the absence of any organic additives. Among them, the Ru complex could provide a TOF (turnover frequency) of 12 000 h–1 and a TON (turnover number) of 350 000 at 90 °C in the HCOOH/HCOONa aqueous solution. In addition to that, efficient production of high-pressure H2 and CO2 (24.0 MPa (3480 psi)) was achieved through the decomposition of formic acid with no formation of CO by this Ru complex. Moreover, well-defined ruthenium (II) PN3P pincer complexes were also developed for the reversible reaction-hydrogenation of carbon dioxide. Excellent product selectivity and catalytic activity with TOF and TON up to 13,000 h-1 and 33,000, respectively, in a THF/H2O biphasic system were achieved. Notably, effective conversion of carbon dioxide from the air into formate was conducted in the presence of an amine, allowing easy product separation and catalyst recycling.

>Magister Scientiae - MSc / This study presents the successful characterization and hydrolysis of magnesium hydride (MgH2) for hydrogen generation. The as-received MgH2 served as a precursor in most of the hydrolysis experiments for H2 generation. The phase-structural and morphological characteristics of the as-received MgH2 were evaluated using scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray dispersive diffraction (XRD) characterization techniques. The hydrogen storage performance of the as-received MgH2 was analysed by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and thermal desorption spectroscopy (TDS) techniques. The hydrolysis of MgH2 was performed in a hydrogen generation reactor operated in a batch mode where the temperature and H2 flow rate were logged.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18641号 / 理博第4020号 / 新制||理||1579(附属図書館) / 31555 / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 吉村 一良, 准教授 前里 光彦 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

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