Multivalent Manganese Hydrazide Gels for Kubas-Type Hydrogen Storage

Hoang, Tuan K.A.; Morris, Leah; Rawson, Jeremy M.; Antonelli, David M.

doi:10.1021/cm300425z

Cited by 25 publications

(28 citation statements)

References 75 publications

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“…The isotherm at 77K increases linearly with the applied pressure without saturation due to the low surface area of the MTF-Fe complex, as has been commonly seen in all low surface area class-two materials. [6][7][8] The similar linear adsorption uptake behaviour is also observed at 298K with a smaller slope, as expected. It is important to note that a linear increase of uptake upon gas compression should be ruled out because the apparatus with an empty sample chamber was thoroughly calibrated at 100 atm prior to the test (Figure 5 a).The isotherm at 77K reveals that the maximum hydrogen storage capacity is approximately 2.3 wt% at 100 atm (21.52 g L −1 ), which is substantially lower than the capacity of high surface porous materials.…”

Section: Doi: 101002/admi201400107supporting

confidence: 85%

“…[6][7][8] Considerably high hydrogen uptake at room temperature was reported in several materials of this class. [6][7][8] Classthree compounds invoke electrostatic interactions stronger than the van der Waals force to induce polarization of adsorbed hydrogen molecules at room temperature. [ 9 ] The adsorption relies on strong cations [ 10 ] or anions [ 11 ] as the active sites in the host compounds.…”

mentioning

confidence: 97%

“…[ 13 ] We note here that the surface area of class two materials is in general substantially smaller than that of class-one and class-three compounds with metal hydrazide gel materials as a typical example. [ 7,8 ] The highest hydrogen capacity of the class-three materials reported to date is 1.01 wt% at room temperature and 90 atm, in spite of the large surface area up to 5109 m 2 g −1 , likely attributed to the limited access of the active metal sites available to H 2 molecules. [ 14 ] Clearly, an appropriate porosity and abundant adsorption sites are two essential attributes required to induce strong physisorption at a near ambient temperature.…”

mentioning

confidence: 99%

“…[ 3,5 ] Class-two materials contain active sites for hydrogen adsorption in the form of under-coordinated metal elements in organometallic complexes. [6][7][8] In these materials, the Kubas type bonding dictates the host-H 2 interaction through the overlapping between the H 2 -σ orbital and an empty orbital of the metal (forward donation), and/or between the H 2 -σ* orbital and an occupied orbital of the metal (back donation). [6][7][8] Considerably high hydrogen uptake at room temperature was reported in several materials of this class.…”

mentioning

confidence: 99%

“…[6][7][8] In these materials, the Kubas type bonding dictates the host-H 2 interaction through the overlapping between the H 2 -σ orbital and an empty orbital of the metal (forward donation), and/or between the H 2 -σ* orbital and an occupied orbital of the metal (back donation). [6][7][8] Considerably high hydrogen uptake at room temperature was reported in several materials of this class. [6][7][8] Classthree compounds invoke electrostatic interactions stronger than the van der Waals force to induce polarization of adsorbed hydrogen molecules at room temperature.…”

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confidence: 99%

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Room Temperature Hydrogen Physisorption on Exposed Metals in A Highly Cross‐Linked Organo‐Iron Complex

Pareek

Zhang

Rohan

et al. 2014

Adv Materials Inter

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ambient temperature range have been observed in a number of materials of this class. [ 9,11,12 ] To date, signifi cant hydrogen uptake at room temperature has only been observed in compounds of the latter two classes but none of the physisorption materials has been found to exhibit a hydrogen capacity that meets the gravimetric and volumetric targets set by the U.S. Department of Energy. [ 13 ] We note here that the surface area of class two materials is in general substantially smaller than that of class-one and class-three compounds with metal hydrazide gel materials as a typical example. [ 7,8 ] The highest hydrogen capacity of the class-three materials reported to date is 1.01 wt% at room temperature and 90 atm, in spite of the large surface area up to 5109 m 2 g −1 , likely attributed to the limited access of the active metal sites available to H 2 molecules. [ 14 ] Clearly, an appropriate porosity and abundant adsorption sites are two essential attributes required to induce strong physisorption at a near ambient temperature.In this Communication, we report an attempt to synthesize a complex with a moderate surface area and relatively dense under-coordinated iron metals for room temperature hydrogen storage via physisorption. The under-coordinated iron atoms, which serve as the active sites for hydrogen adsorption, are accommodated in a melamine-terephthaldehyde framework (MTF-Fe). The synthesized complex displays a wide range of nano-pores with a specifi c surface area up to 175 m 2 g −1 ; each iron atom is under-coordinated by formally forming only four bonds with the organic framework and is exposed on the walls of the nano-pores. This architecture facilitates diffusion and adsorption of hydrogen molecules in the network and enables storage to be realized via PSA at a near ambient temperature. Indeed, a measurement of hydrogen uptake yields a gravimetric storage capacity up to 1.7 wt% at 298K and 100 atm, substantially higher than the value for most MOF compounds and high surface area carbon materials and comparable to the hydrogen capacity of the best hydrogen physisorption materials reported to date under similar conditions. [ 5,14,15 ] Melamine-terephthaldehyde based compounds with crosslinked porous organic frameworks were successfully synthesized recently. [ 16,17 ] These materials exhibit high thermal stability, large surface areas and high porosity. Similar to most MOF compounds, the melamine-terephthaldehyde based complexes display virtually no activity toward hydrogen at a near ambient temperature due to lack of active sites. By adopting a similar synthesis protocol, schematically shown in Scheme 1 , but incorporating under-coordinated organo-iron species active to hydrogen molecules in the precursors, a material with a moderate surface area but numerous coordinatively unsaturated iron ions exposed on the walls of a polymeric network was then formed.The development of materials capable of storing hydrogen in high capacity via physical interaction at near ambient temperatures has long been recogni...

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Section: Doi: 101002/admi201400107supporting

confidence: 85%

mentioning

confidence: 97%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Room Temperature Hydrogen Physisorption on Exposed Metals in A Highly Cross‐Linked Organo‐Iron Complex

Pareek

Zhang

Rohan

et al. 2014

Adv Materials Inter

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Functional Materials for Gas Storage. PartII: Hydrogen and Methane

Reguera

2017

Handbook of Solid State Chemistry

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SummaryThe second part of this overview on functional materials for gases storage discusses hydrogen and methane storage in porous solids and clathrates. For hydrogen, the dissociative storage as hydrides and spillover is also considered. Methane is the most attractive energy vector in a context of energetic transition, from an extensive use of oil and its derivatives as fuel to an economy based on hydrogen as energy bearer. During the last decades, tens of thousands of porous solids have been prepared and evaluated as absorbents, including inorganic, metal‐organic, and organic solids, mainly for molecular hydrogen storage; many of them also considered for methane storage. To rationalize that huge volume of information, the available data are critically reviewed according to the nature of the guest–host interactions that determine the adsorption forces and the related adsorption heats. Clathrates of hydrogen and methane represent a promise route of reversible storage, particularly those clathrates where the cages are formed by water molecules (hydrates). The largest global reserves of methane are found as hydrates below the oceans floors.

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High‐Pressure Raman and Calorimetry Studies of Vanadium(III) Alkyl Hydrides for Kubas‐Type Hydrogen Storage

et al. 2016

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Reversible hydrogen storage under ambient conditions has been identified as a major bottleneck in enabling a future hydrogen economy. Herein, we report an amorphous vanadium(III) alkyl hydride gel that binds hydrogen through the Kubas interaction. The material possesses a gravimetric adsorption capacity of 5.42 wt % H2 at 120 bar and 298 K reversibly at saturation with no loss of capacity after ten cycles. This corresponds to a volumetric capacity of 75.4 kgH2 m(-3) . Raman experiments at 100 bar confirm that Kubas binding is involved in the adsorption mechanism. The material possesses an enthalpy of H2 adsorption of +0.52 kJ mol(-1) H2 , as measured directly by calorimetry, and this is practical for use in a vehicles without a complex heat management system.

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Multivalent Manganese Hydrazide Gels for Kubas-Type Hydrogen Storage

Cited by 25 publications

References 75 publications

Room Temperature Hydrogen Physisorption on Exposed Metals in A Highly Cross‐Linked Organo‐Iron Complex

Room Temperature Hydrogen Physisorption on Exposed Metals in A Highly Cross‐Linked Organo‐Iron Complex

Functional Materials for Gas Storage. PartII: Hydrogen and Methane

High‐Pressure Raman and Calorimetry Studies of Vanadium(III) Alkyl Hydrides for Kubas‐Type Hydrogen Storage

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