Liquid hydrogen

Summary

Liquid hydrogen (H2(l)) is the liquid state of the element hydrogen. Hydrogen is found naturally in the molecular H2 form. To exist as a liquid, H2 must be cooled below its critical point of 33 K. However, for it to be in a fully liquid state at atmospheric pressure, H2 needs to be cooled to . A common method of obtaining liquid hydrogen involves a compressor resembling a jet engine in both appearance and principle. Liquid hydrogen is typically used as a concentrated form of hydrogen storage. Storing it as liquid takes less space than storing it as a gas at normal temperature and pressure. However, the liquid density is very low compared to other common fuels. Once liquefied, it can be maintained as a liquid in thermally insulated containers. There are two spin isomers of hydrogen; whereas room temperature hydrogen is mostly orthohydrogen, liquid hydrogen consists of 99.79% parahydrogen and 0.21% orthohydrogen. Hydrogen requires a theoretical minimum of 3.3 kWh/kg to liquefy, and 3.9 kWh/kg including converting the hydrogen to the para isomer, but practically generally takes 10-13 kWh/kg compared to a 33 kWh/kg heating value of hydrogen. In 1885, Zygmunt Florenty Wróblewski published hydrogen's critical temperature as ; critical pressure, 13.3 atmospheres; and boiling point, . Hydrogen was liquefied by James Dewar in 1898 by using regenerative cooling and his invention, the vacuum flask. The first synthesis of the stable isomer form of liquid hydrogen, parahydrogen, was achieved by Paul Harteck and Karl Friedrich Bonhoeffer in 1929. Spin isomers of hydrogen The two nuclei in a dihydrogen molecule can have two different spin states. Parahydrogen, in which the two nuclear spins are antiparallel, is more stable than orthohydrogen, in which the two are parallel. At room temperature, gaseous hydrogen is mostly in the ortho isomeric form due to thermal energy, but an ortho-enriched mixture is only metastable when liquified at low temperature. It slowly undergoes an exothermic reaction to become the para isomer, with enough energy released as heat to cause some of the liquid to boil.

Official source

https://en.wikipedia.org/wiki/Liquid_hydrogen

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Molecular Engineering of Electrode Surfaces for Electrocatalysis

Patrick Eduard Alexa

Electrocatalysts play an important part on the route towards environmental friendly energy sources. They support modern technologies like fuel cells to move further away from the utilization of fossil fuels and the resulting CO2 emission into our atmosphere. The main principle of such energy conversion technologies is to store chemical energy within chemical bonds and to release it as electric energy to fulfill the energy demand of today's society. However energy conversion chemistry in such technologies requires catalysts in order to be effective by providing an alternative reaction pathway that lowers activation energies and maximizes the energy output. Providing suitable catalyst surfaces requires a fundamental knowledge of the interaction of reactants and reaction intermediates with the catalyst surfaces. This concern is addressed in this thesis by fabricating specifically tailored molecular components on metal surfaces, which act as organic/inorganic hybrid electrodes for various energy conversion reactions in electrocatalysis. Characterizing the electrode surface is crucial in order to identify active sites of the catalyst. The molecular structure is investigated by surface sensitive techniques, such as STM and XPS in combination with a home-build transfer system, which enables electrode fabrication in UHV and electrocatalytic experiments in a liquid environment. A detailed characterization of organic polymer components on electrode surfaces is obtained by combining experimental data with MD simulations. The morphology of polymer networks can be successfully mimicked and depending on the chemical composition and the structure, spatial correlations on short length scales are reported. Hybrid electrodes with organic polymer co-catalysts reveal an increased catalytic activity for the HER by providing suitable docking sites that act as catalytic active sites. Reactants and reaction intermediates are stabilized via hydrogen bonding, which results in a higher catalytic turnover. The specific designed structure of the organic co-catalyst helps to identify a fraction of the reaction mechanism and highlights the importance of molecular components in electrocatalysis. The utilization of organic units on electrocatalysts provides also an excellent opportunity in order to use single metal atoms as catalysts. Engineering large pi-systems has no significant impact on the ORR activity, while the distance between active sites and the underlying electrode are crucial for enhancing the catalytic activity. A significant factor in using molecular components in electrocatalysis is the stability of the organics. Using electrografting allows to design organic/inorganic hybrid electrodes with covalent bonds between the molecular component and the metal substrate. Attaching empty porphyrin molecules to substrates introduces a powerful technique in molecular engineering, since empty porphyrin cycles can be metallized with various metal centers that can act as electrocatalysts for different electrochemical reactions. In summary, this thesis provides multiple engineering aspects, which are useful in designing molecular components on metal electrodes for energy conversion. Such hybrid catalyst surfaces are capable of improving the catalytic activity and allow to study the mechanism of catalytic reactions. Implementing organic components provides new routes for tailoring novel materials, which deliver new insight into the complex field of electrocatalysis.

EPFL2020

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The main difference between the past energy economy during the industrialization period which was mainly based on mining of fossil fuels, e.g. coal, oil and methane and the future energy economy based on renewable energy is the requirement for storage of the energy fluxes. Renewable energy, except biomass, appears in time- and location-dependent energy fluxes as heat or electricity upon conversion. Storage and transport of energy requires a high energy density and has to be realized in a closed materials cycle. The hydrogen cycle, i.e. production of hydrogen from water by renewable energy, storage and use of hydrogen in fuel cells, combustion engines or turbines, is a closed cycle. However, the hydrogen density in a storage system is limited to 20 mass% and 150 kg/m(3) which limits the energy density to about half of the energy density in fossil fuels. Introducing CO, into the cycle and storing hydrogen by the reduction of CO, to hydrocarbons allows renewable energy to be converted into synthetic fuels with the same energy density as fossil fuels. The resulting cycle is a closed cycle (CO2 neutral) if CO, is extracted from the atmosphere. Today's technology allows CO, to be reduced either by the Sabatier reaction to methane, by the reversed water gas shift reaction to CO and further reduction of CO by the Fischer Tropsch synthesis (FTS) to hydrocarbons or over methanol to gasoline. The overall process can only be realized on a very large scale, because the large number of by-products of FTS requires the use of a refinery. Therefore, a well-controlled reaction to a specific product is required for the efficient conversion of renewable energy (electricity) into an easy to store liquid hydrocarbon (fuel). In order to realize a closed hydrocarbon cycle the two major challenges are to extract CO, from the atmosphere close to the thermodynamic limit and to reduce CO2 with hydrogen in a controlled reaction to a specific hydrocarbon. Nanomaterials with nanopores and the unique surface structures of metallic clusters offer new opportunities for the production of synthetic fuels.

Schweizerische Chemische Gesellschaft2015

Comprehensive studies of gas-solid reactions require the in-situ interaction of the gas at a pressure beyond the operating pressure of ultrahigh vacuum (UHV) X-ray photoelectron spectroscopy (XPS). The recent progress of near ambient pressure XPS allows to dose gases to the sample up to a pressure of 20 mbar. The present work describes an alternative to this experimental challenge, with a focus on H-2 as the interacting gas. Instead of exposing the sample under investigation to gaseous hydrogen, the sample is in contact with a hydrogen permeation membrane, through which hydrogen is transported from the outside to the sample as atomic hydrogen. Thereby, we can reach local hydrogen concentrations at the sample inside an UHV chamber, which is equipped with surface science tools, and this corresponds to a hydrogen pressure up to 1 bar without affecting the sensitivity or energy resolution of the spectrometer. This experimental approach is validated by two examples, that is, the reduction of a catalyst precursor for CO2 hydrogenation and the hydrogenation of a water reduction catalyst for photocatalytic H-2 production, but it opens the possibility of the new in situ characterisation of energy materials and catalysts. (C) 2015 AIP Publishing LLC.

American Institute of Physics2015