Heat of Adsorption for Hydrogen in Microporous High‐Surface‐Area Materials

Schmitz, Barbara; Müller, Ulrich; Trukhan, Natalia; Schubert, Markus M.; Férey, Gérard; Hirscher, Michael

doi:10.1002/cphc.200800463

Cited by 159 publications

(118 citation statements)

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“…This process is called dissociation and chemisorption. The chemisorption energy is typically in the range of E Chem ≈ 20 -150 kJ/mol H 2 and thus significantly higher than the respective energy for physisorption which is in the order of 4-6 kJ/mol H 2 for carbon based high surface materials (Schmitz et al, 2008). Fig.…”

Section: Basics Of Hydrogen Storage In Metal Hydridesmentioning

confidence: 93%

Thermodynamics of Metal Hydrides: Tailoring Reaction Enthalpies of Hydrogen Storage Materials

Dornheim¹

2011

Thermodynamics - Interaction Studies - Solids, Liquids and Gases

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Section: Basics Of Hydrogen Storage In Metal Hydridesmentioning

confidence: 93%

Thermodynamics of Metal Hydrides: Tailoring Reaction Enthalpies of Hydrogen Storage Materials

Dornheim¹

2011

Thermodynamics - Interaction Studies - Solids, Liquids and Gases

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“…Experimentally, however, a correlation between pore size and heat of adsorption is observed. 42,43 Ref. 28 adjusted Bhatia and Myers' formula for the optimal heat of adsorption in the context of hydrogen storage by taking into account the positive correlation found between enthalpy and entropy changes upon adsorption.…”

Section: Model 2 and The Entropy-enthalpy Correlationmentioning

confidence: 99%

Optimizing nanoporous materials for gas storage

Simon

Kim

Lin

et al. 2014

Phys. Chem. Chem. Phys.

119

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aIn this work, we address the question of which thermodynamic factors determine the deliverable capacity of methane in nanoporous materials. The deliverable capacity is one of the key factors that determines the performance of a material for methane storage in automotive fuel tanks. To obtain insights into how the molecular characteristics of a material are related to the deliverable capacity, we developed several statistical thermodynamic models. The predictions of these models are compared with the classical thermodynamics approach of Bhatia and Myers [Bhatia and Myers, Langmuir, 2005, 22, 1688] and with the results of molecular simulations in which we screen the International Zeolite Association (IZA) structure database and a hypothetical zeolite database of over 100 000 structures. Both the simulations and our models do not support the rule of thumb that, for methane storage, one should aim for an optimal heat of adsorption of 18.8 kJ mol À1. Instead, our models show that one can identify an optimal heat of adsorption, but that this optimal heat of adsorption depends on the structure of the material and can range from 8 to 23 kJ mol À1. The different models we have developed are aimed to determine how this optimal heat of adsorption is related to the molecular structure of the material.

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“…35 The adsorption of hydrogen at 293 K and 1 bar amounts to a meager ∼0.06 wt% (Fig. S29 ‡), but it significantly exceed the interpolated value for MOF-5 43 or HKUST-1 (0.1 wt% at 20 bar; 35 the dependence is practically linear in the 1-20 bar pressure) and also much more than the measured ∼0.01 wt% (298 K, 1 bar) for single walled nanotubes (SWNT) 44 or for active carbons (the interpolated value is 8 × 10 −3 -1 × 10 −2 wt% at 298 K). 45 Interestingly, the affinity towards hydrogen is strong and the desorption is almost absent on the time-scale of minutes, however it might be only a kinetic effect.…”

Section: Sorption Studies Of Degassed [Cu 4 CL 4 L(dmf) 5 ]·Dmfmentioning

confidence: 99%

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

et al. 2014

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·62 ·8}, gis or gismondine underlying net, where the role of the tetrahedral nodes is served by the coordination bonded clusters and the adamantane moiety. 3 (P2 1 /n) has a porous structure composed of coordination bonded layers with a (4·8 2 ) fes topology joined via trans-{Zn- The high number of donor functions endows the tetrazolate function with a capability to sustain unusually high number of coordination bonded arrangements ( patterns) 7 compared to other azolates. In the case of simple rigid ligands it is a prerequisite for assembly of a highly symmetric framework, with a † Dedicated to Prof. Marius Andruh on the occasion of his 60th birthday. View Article OnlineView Journal | View Issue significant probability of isomerism. Indeed, the linear 1,4-benzeneditetrazole (H 2 BDT) 8 and flat triangular 1,3,5-benzene- hedral' tetrazolates and involving chloride anions as coligands, serve as an interesting example of variability of coordination-bonded cluster geometry and size due to involvement of short halido bridges. 16,20 It was conjectured that mixed tetrazolato/halido coordination polymers constitute an interesting compound class with 'scalable' multinuclear clusters, 20 which are interesting either as robust SBUs or possibly as functional magnetic units. In this contribution we probed the practically unexplored 1,3,5,7-tetrakis(tetrazol-5yl)adamantane ligand (H 4 L) as a building block for coordination polymers using conditions favoring formation of tetrazolato/halido clusters (Scheme 1). This ligand in anionic form has one of the highest density of donor sites achievable for a 'tetrahedral' ligand, which is a prerequisite for rich coordination and structural chemistry of derived coordination-bonded frameworks. Results and discussion The ligandUniversal rigid molecular platforms with tetrahedral symmetry are typically limited to tetraphenylmethane (including 9,9′-spirobifluorene) and adamantane, as well as their phenyl augmented and heteroatom-substituted analogues.14 Adamantane is the smallest tetrahedral platform next only to quaternary carbon, while the latter has inherent steric limitations. Adamantane is widely used for the synthesis of organic polymers (recently with an emphasis on porous organic polymers and covalent organic frameworks), 22 dendrimers, 23 and molecular entities for supramolecular synthesis 24 and nanotechnology. 25Compared to tetraphenylmethane, whose modification is standard and facile, the chemistry of adamantanes is peculiar, at times cumbersome, but offering synthetic opportunities as well. For example adamantane could be selectively brominated in bridgehead positions to afford mono-to tetra-substituted adamantanes in high yields. 26 However, 1,3,5,7-tetrabromoadamantane is the most chemically inert entity in the row and the substitution of halogens via the S N1 mechanism demands harsh conditions. It was not only until the recent paper of Lee et al.,27 in which photochemical cyanodebromination of 1,3,5,7-tetrabromoadamantane was described that a facile route to various tetra...

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Heat of Adsorption for Hydrogen in Microporous High‐Surface‐Area Materials

Cited by 159 publications

References 28 publications

Thermodynamics of Metal Hydrides: Tailoring Reaction Enthalpies of Hydrogen Storage Materials

Thermodynamics of Metal Hydrides: Tailoring Reaction Enthalpies of Hydrogen Storage Materials

Optimizing nanoporous materials for gas storage

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

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Heat of Adsorption for Hydrogen in Microporous High‐Surface‐Area Materials

Cited by 159 publications

References 28 publications

Thermodynamics of Metal Hydrides: Tailoring Reaction Enthalpies of Hydrogen Storage Materials

Thermodynamics of Metal Hydrides: Tailoring Reaction Enthalpies of Hydrogen Storage Materials

Optimizing nanoporous materials for gas storage

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl2(M = Mn, Cu, Zn, Cd)

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1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)