Neutron scattering studies of materials for hydrogen storage

Klein, Ryan A.; Evans, Hayden A.; Trump, Benjamin A.; Udovic, Terrence J.; Brown, Craig M.

doi:10.1016/b978-0-12-823144-9.00028-5

Cited by 8 publications

(13 citation statements)

References 562 publications

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“…and S17 †), which possibly explains why this is the initial adsorption site. At this loading concentration, the adsorption distances are 2.66(8) Åfrom the D 2 molecule to the centroid of the imidazolate ring and 2.68(8) Å to the centroid of the benzene ring. These close adsorption distances indicate relatively strong D 2 -arene interactions.…”

mentioning

confidence: 90%

“…Among porous adsorbates, metal-organic frameworks (MOFs) stand out as extremely promising for hydrogen storage applications. [2][3][4][5][6][7][8] MOFs are porous crystalline materials composed of polytopic organic linkers bridging inorganic nodes. Some MOFs display framework exibility.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, an enhanced understanding of the structural causes of hydrogen-induced phase changes is needed to enable rational synthetic tuning of the pressure and temperature step conditions in candidate storage materials. 8,47,48 To enhance our structural understanding of hydrogeninduced phase changes in porous frameworks we turned to another archetypal exible material, ZIF-7 (Zn(benzimidazolate) 2 , SOD, ZnC 14 H 10 N 4 ), in which ditopic benzimidazolate linkers bridge tetrahedrally coordinated Zn(II) sites. 23,49,50 The water-solvated phase of ZIF-7 crystallizes in the trigonal R 3 space group (Fig.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structural resolution and mechanistic insight into hydrogen adsorption in flexible ZIF-7

Klein

Shulda

Maguères³

et al. 2021

Chem. Sci.

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confidence: 90%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structural resolution and mechanistic insight into hydrogen adsorption in flexible ZIF-7

Klein

Shulda

Maguères³

et al. 2021

Chem. Sci.

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“…One promising class of materials for hydrogen storage applications are the metal hydrides, which chemisorb molecular hydrogen and store the H atoms in the interstices of the metal lattice [4]. Currently, the best metal hydride materials suffer from low reversible hydrogen storage capacities at operationally relevant conditions [5,6]. Although the volumetric capacity in metal hydrides is high-exceeding that of liquid H 2 in many cases [7]-it is fundamentally limited based on an empirical rule known as the Switendick-Westlake criterion [8,9].…”

Section: Introductionmentioning

confidence: 99%

Neutron Vibrational Spectroscopic Evidence for Short H···H Contacts in the RNiInH_1.4;1.6 (R = Ce, La) Metal Hydride

Klein

Balderas‐Xicohténcatl

Mæhlen

et al. 2022

Neutron News

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Intermetallic metal hydrides are critical materials for hydrogen storage applications, however, metal hydrides with greater storage capacities are still needed. Within metal hydrides, the volumetric storage capacities are limited by the number of hydrogen-accommodating interstitial sites which can be simultaneously occupied given a minimum hydride nearest-neighbor distance of ≈ 2.1 Å, according to the Switendick-Westlake criterion. To date, violations of this criterion are rare. Perhaps the most well studied compounds violating this criterion are the RNiInH x compounds (R = Ce, La, Nd). Previous neutron diffraction studies on the deuterated species revealed the presence of Ni-DYet there are no neutron vibrational spectroscopic investigations reported for these atypical hydrides. Here we use neutron vibrational spectroscopy (NVS) measurements to probe the hydrogen dynamics in LaNiInH x (x = 0.67, 1.6) and CeNiInH 1.4 . For x > 0.67, the presence of close H•••H contacts yields two related features in the vibrational spectrum centered near ≈ 90 meV corresponding to the oscillations of paired H atoms simultaneously occupying neighboring R 3 Ni tetrahedra. Notably, these features are energetically distinct from comparable vibrational motions for "unpaired" H atoms when x ≤ 0.67. To compare, we also present powder neutron diffraction and NVS measurements for the newly characterized, chemically similar Sn compounds CeNiSnH, CeNiSnH 2 , and CeNiSnD 2 . These compounds also contain R 3 Ni tetrahedra, however, the H-occupied tetrahedra are well separated from each other with the closest H•••H distances exceeding 2.1 Å, and the Switendick-Westlake criterion is not violated. Consequently, the spectral signature of the close H•••H contacts is absent in these hydrides.

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Multivariate Flexible Framework with High Usable Hydrogen Capacity in a Reduced Pressure Swing Process

et al. 2023

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Step-shaped adsorption–desorption of gaseous payloads by flexible metal–organic frameworks can facilitate the delivery of large usable capacities with significantly reduced energetic penalties. This is desirable for the storage, transport, and delivery of H2, as prototypical adsorbents require large swings in pressure and temperature to achieve usable capacities approaching their total capacities. However, the weak physisorption of H2 typically necessitates undesirably high pressures to induce the framework phase change. As de novo design of flexible frameworks is exceedingly challenging, the ability to intuitively adapt known frameworks is required. We demonstrate that the multivariate linker approach is a powerful tool for tuning the phase change behavior of flexible frameworks. In this work, 2-methyl-5,6-difluorobenzimidazolate was solvothermally incorporated into the known framework CdIF-13 (sod-Cd(benzimidazolate)2), resulting in the multivariate framework sod-Cd(benzimidazolate)1.87(2-methyl-5,6-difluorobenzimidazolate)0.13 (ratio = 14:1), which exhibited a considerably reduced stepped adsorption threshold pressure while maintaining the desirable adsorption–desorption profile and capacity of CdIF-13. At 77 K, the multivariate framework exhibits stepped H2 adsorption with saturation below 50 bar and minimal desorption hysteresis at 5 bar. At 87 K, saturation of step-shaped adsorption occurs by 90 bar, with hysteresis closing at 30 bar. These adsorption–desorption profiles enable usable capacities in a mild pressure swing process above 1 mass %, representing 85–92% of the total capacities. This work demonstrates that the desirable performance of flexible frameworks can be readily adapted through the multivariate approach to enable efficient storage and delivery of weakly physisorbing species.

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Neutron scattering studies of materials for hydrogen storage

Cited by 8 publications

References 562 publications

Structural resolution and mechanistic insight into hydrogen adsorption in flexible ZIF-7

Structural resolution and mechanistic insight into hydrogen adsorption in flexible ZIF-7

Neutron Vibrational Spectroscopic Evidence for Short H···H Contacts in the RNiInH_1.4;1.6 (R = Ce, La) Metal Hydride

Multivariate Flexible Framework with High Usable Hydrogen Capacity in a Reduced Pressure Swing Process

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Neutron scattering studies of materials for hydrogen storage

Cited by 8 publications

References 562 publications

Structural resolution and mechanistic insight into hydrogen adsorption in flexible ZIF-7

Structural resolution and mechanistic insight into hydrogen adsorption in flexible ZIF-7

Neutron Vibrational Spectroscopic Evidence for Short H···H Contacts in the RNiInH1.4;1.6 (R = Ce, La) Metal Hydride

Multivariate Flexible Framework with High Usable Hydrogen Capacity in a Reduced Pressure Swing Process

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Neutron Vibrational Spectroscopic Evidence for Short H···H Contacts in the RNiInH_1.4;1.6 (R = Ce, La) Metal Hydride