Guide Materials for the Hydrogen Economy

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Patent Foundation to patent their discovery. Patent Foundation. Phillips and Dr. Shivaram have made an incredible breakthrough in the area of hydrogen absorption. Bellave S. Shivaram and Adam B. Phillips, the U. Department of Energy. Materials provided by University of Virginia.

Note: Content may be edited for style and length. Science News. Story Source: Materials provided by University of Virginia. ScienceDaily, 13 November University of Virginia. Thereby, it is intended that these metal sites act as catalysts, in order to break the H—H bond, so that the adsorbed species are hydrogen atoms rather than the molecule itself. While theoretical studies claim the feasibility of this method, experiments have not yet been crowned with success [ , ]. In addition, the formation of chemical bonds to the host material has to be taken into account so that high temperatures could be necessary for releasing the hydrogen [ ].

Also in the case of unsaturated adsorption centers, the chemical composition of the material host is changed by introducing other species like, for example, metals. However, their interaction with the hydrogen molecule is weaker and limited to increase the adsorption potential. This is accomplished by donation of charge between the molecules and the functionalized interaction sites [ ]. This approach has been proven to be partially successful. However, these high values may be caused by mechanisms different from the adsorption process.

The main disadvantage of those first two methods is that additional heavy species are introduced into the porous material. This decreases the specific surface area and pore volumes, prejudicing the gravimetric storage capacity of the material. The third method, decreasing the pore sizes of the material, manages without the introduction of additional species. Here, the concept is to build a very narrow porosity in which the hydrogen molecule can simultaneously interact with multiple pore walls. Due to their proximity, the adsorption potentials of opposed pore walls overlap, resulting in an amplified attraction.

However, such correlation was found to be more precise with the total volume of micropores [ 45 , , ]. At room temperature, the optimum pore size was found to be around 0. This coincides with an overlapping of two carbon-hydrogen potentials, similar to the one shown in Figure 9. A pore of this size is sufficient for accommodating two layers of hydrogen molecules [ ]. The amount of pores which are narrower than 0. For hydrogen adsorption amounts at room temperature, a better correlation is achieved with this value than with the total micropore volume or the BET surface area [ 45 , — , — ].

Numerous kinds of materials have been investigated as adsorbents for hydrogen. These include carbon-based materials activated carbons, carbon nanotubes, nanofibers, fullerenes, carbons from templates, etc. In the following, a brief overview of the different classes of materials as well as their performance for hydrogen storage is given.

Zeolites are aluminosilicates which can accommodate a wide variety of cations [ ]. These materials can be found naturally or can be produced synthetically [ ]. Due to their crystalline structure, zeolites have a very defined porous structure. They are used in numerous industrial applications, for example as detergents, catalysts, desiccants, molecular sieves, or for water purification as well as gas separation and purification through pressure swing adsorption PSA [ — ].

Zeolites were among the first porous materials which have been investigated for hydrogen storage purposes [ — ]. However, due to their low porosity, hydrogen adsorption amounts are limited. Thus, less than 1. Theoretical calculations reveal that, even under ideal conditions, adsorption amounts are limited to 2. Some natural or synthetic oxides like silica and alumina can also reveal high porosity which often has a high contribution of mesopores.

Due to this characteristic, these materials find a lot of applications in catalysis, separations, sensors, drug delivery, optical devices, and molecular sieves [ ]. However, their porous structure results inappropriate for hydrogen storage, and less than 0. However, their low material density of typically around 0. Together with their inappropriate pore size distribution, these materials can be regarded unsuitable as hydrogen storage medium [ , ].

More recently, also noncarbon nanotubes have been proposed for hydrogen storage [ ]. Boron nitride BN nanotubes, for instance, were claimed to have advantages over carbon nanotubes CNTs and to adsorb up to 2. Another class of materials which recently were proposed for hydrogen storage application are porous polymers [ — ]. Polymers of intrinsic microporosity PIM are another approach to introduce porosity into polymers. Coordination polymers like metal-organic frameworks MOFs and covalent organic frameworks COVs are a different kind of porous polymer.

1. Introduction

Similar to zeolites, these materials are of highly crystalline nature. However, different from zeolites, the structure of these frameworks is composed of lighter elements, giving rise to higher specific porosity. Thus, MOF structures are built by metal ion clusters which are connected by organic linking groups. In the case of COFs, aromatic rings are the primary structural element [ ]. The building blocks are linked by strong covalent bonds, resulting in a rigid structure which contains exclusively very light elements like H, B, C, N, or O.

The crystallinity of coordination polymers allows for an exact control of their porosity. A common strategy to achieve high surface areas in organic framework materials is to increase the size of the organic linkers [ ]. However, this increases also the pore sizes of the structure which may be a problem for hydrogen adsorption at room temperature where small pores are advantageous.

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In addition, the low density of coordination polymers leads to relatively low volumetric storage density. Furthermore, MOFs are relatively sensitive to conditions of high temperature, mechanical pressure, and humidity which can lead to degradation of the material [ , ]. Activated carbon AC is an interesting and well-known adsorbent with a highly adaptable porosity. Activated carbon materials are a form of carbon which does not occur naturally and which has to be synthesized technically. The porosity in ACs can cover a wide range of pore sizes and can be controlled by adjusting the activation parameters.

Furthermore, the characteristics of the adsorbent can be adjusted by manipulating its surface chemistry. Activated carbon materials can be used in numerous applications, for example, in liquid and gas phase treatments e. Together with zeolites, carbon materials were among the first adsorbents studied for hydrogen storage [ , ].

Thereby, research was focused on activated carbons ACs with high specific surface areas. Since the early days, a number of carbonaceous nanomaterials have been discovered, for example, fullerenes, multiwalled nanotubes MWNTs , and single-walled nanotubes SWNTs. Currently, it is concluded that adsorption on nanomaterials is simply due to physisorption. Due to their low porosity in comparison with other carbon adsorbents like activated carbons, the latter perform better in terms of hydrogen storage [ 45 ].

Models for estimating the maximum hydrogen capacity of activated carbons often utilize graphene sheets. If the graphene planes are separated by slip pores of idealized size, up to 9. Nevertheless, real activated carbons are highly disordered, giving rise to other adsorption sites, for example, at graphene edges, and reveal a distribution of different pore sizes. A lot of data can be found for commercial activated carbon materials [ , ]. However, fewer studies have been carried out regarding synthesis and analysis of activated carbon materials that are specially tailored for hydrogen storage.

On zeolite-templated carbon 6. At room temperature, maximum adsorption of almost 1.

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Strong efforts have been made in order to reach the targets for hydrogen storage in mobile applications which were established by bodies like the DOE. Yet, none of the investigated technologies currently fulfills all of the requirements. However, this technology may not be appropriate for reaching the ambitious ultimate targets, and security concerns exist over the high pressures involved. The use of liquid hydrogen is handicapped by the energy intensive liquefaction process as well as hydrogen boil-off.

The storage of hydrogen inside materials could be advantageous in a number of aspects. Metal hydrides and other compounds with chemisorbed hydrogen can reach high capacities. However, one has to bear in mind that storage capacities of the materials alone have to be significantly higher according to the established targets which are system-based.

A promising alternative could be hydrogen storage by physisorption in porous materials. The challenges for designing suitable adsorbents are 1 increasing their porosity, 2 tuning of pore sizes, 3 optimization of adsorption potentials, and 4 enhancement of the bulk material density in order to reach high volumetric capacities. The authors confirm that no conflict of interests exists and that they do not have any direct financial relation with any of the commercial identities mentioned in the paper. Journal of Renewable Energy.

Journal Menu. Special Issues Menu. Subscribe to Table of Contents Alerts. Table of Contents Alerts. Abstract A hydrogen economy is needed, in order to resolve current environmental and energy-related problems. Figure 1: Global temperature red and CO 2 emissions blue over the past decades [ 14 — 16 ]. Figure 2: Discovery of conventional oil reserves blue and oil consumption red [ 5 ].

Table 2: Comparison of fuel safety properties in air [ 18 , 24 , 25 , 27 ]. Figure 3: Heat of combustion on a gravimetric basis, shown for various gaseous, liquid, and solid fuels under standard conditions. The ranges of values were obtained by utilizing a multitude of sources [ 18 , 28 — 38 ]. Figure 4: Heat of combustion on a volumetric basis, shown for various gaseous, liquid, and solid fuels under standard conditions. Table 3: DOE hydrogen storage targets for light-duty vehicles [ 41 ]. Figure 5: Schematic diagram of a type 4 pressure vessel and its components for gaseous hydrogen storage Quantum Technologies, Inc.

Reprinted from [ 26 ], with permission from Elsevier. Reprinted from [ 57 ], with permission from International Association of Hydrogen Energy. Figure 7: Comparison of volumetric fuel densities for different hydrogen storage technologies: compressed hydrogen GH2 at room temperature for 0. Figure 8: Density diagram for hydrogen, including the DOE targets for volumetric storage density. Thermo-physical data was obtained from NIST [ ].

Table 5: Lenard-Jones constants for the carbon-hydrogen interaction. Figure 9: Lennard-Jones potential of the carbon-hydrogen interaction. Values for and were taken from [ ]. References Core Writing Team, R. Pachauri, and A. View at Google Scholar M. View at Google Scholar K. Aleklett and C. Hirsch, R. Bezdek, and R. View at Google Scholar A. Boden, G. Marland, and R. Hansen, R. Ruedy, M. Sato, and K. Zumerchik, Ed. King, Ed. Schlapbach and A. Bain and D. View at Google Scholar E. Tzimas, C. Filiou, S. Peteves, and J. View at Google Scholar R. Dean, Ed.

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