Natural supramolecular crystals with excessive hydrogen storage efficiency may improve fuel-cell car effectivity – TechnoNews

Catenation evaluation and crystal superstructures of RP-H100 and RP-H101. Credit score: Nature Chemistry (2024). DOI: 10.1038/s41557-024-01622-w

Hydrogen is usually seen because the gas of the long run on account of its zero-emission and excessive gravimetric power density, which means it shops extra power per unit of mass in comparison with gasoline. Its low volumetric density, nevertheless, means it takes up a considerable amount of house, posing challenges for environment friendly storage and transport.

In an effort to tackle these deficiencies, hydrogen have to be compressed in tanks to 700-bar strain, which is extraordinarily excessive. This example not solely incurs excessive prices but in addition raises security considerations.

For hydrogen-powered fuel-cell autos (FCVs) to turn into widespread, the US Division of Power (DOE) has set particular targets for hydrogen storage programs: 6.5% of the storage materials’s weight needs to be hydrogen (gravimetric storage capability of 6.5 wt%), and one liter of storage materials ought to maintain 50 grams of hydrogen (a volumetric storage capability of fifty g L‒1). These targets be sure that autos can journey cheap distances with out extreme gas.

One promising technique to attain these targets is to develop porous adsorbent supplies, corresponding to metal-organic frameworks (MOFs), covalent natural frameworks (COFs), and porous natural polymers (POPs). All these supplies share a standard characteristic: they possess a porous construction that enables them to successfully entice and retailer hydrogen fuel. This strategy additionally goals to facilitate hydrogen storage at decrease strain, corresponding to inside 100 bar.

Regardless of developments in surpassing the DOE’s gravimetric goal, many adsorbent supplies nonetheless battle to satisfy volumetric capability wants, and few can stability each volumetric and gravimetric targets. From an industrial standpoint, volumetric capability is extra essential than gravimetric capability, as car storage tanks have restricted house.

A hydrogen storage system’s quantity immediately impacts the driving vary of FCVs. Due to this fact, creating hydrogen adsorbents that maximize volumetric capability whereas sustaining wonderful gravimetric capability is important. Attaining this objective entails balancing a excessive volumetric and gravimetric floor space throughout the identical materials.

Researchers are investigating numerous supplies for hydrogen storage, with natural supramolecular crystals meeting from natural molecules by way of noncovalent interactions, being a promising possibility on account of their recyclability. Their potential stays largely untapped, nevertheless, as a result of designing supramolecular crystals with balanced excessive gravimetric and volumetric floor areas, whereas sustaining stability, is troublesome.

A phenomenon referred to as catenation, which entails mechanically interlocked networks in porous supplies, usually enhances stability. Catenation, nevertheless, usually reduces floor space by blocking accessible surfaces, making the fabric much less porous and customarily undesirable for hydrogen storage. Efforts are normally made to reduce or keep away from it.

Interpenetration evaluation of RP-H100 and RP-H101. Credit score: Nature Chemistry (2024). DOI: 10.1038/s41557-024-01622-w

To unlock the potential of supramolecular crystals for hydrogen storage, a collaborative analysis workforce led by Professor Fraser STODDART, together with Analysis Assistant Professors, Dr. Chun Tang, Dr. Ruihua Zhang from the Division of Chemistry, The College of Hong Kong (HKU), and Professor Randall Snurr from the Division of Chemical and Organic Engineering, Northwestern College, US, demonstrated a managed “point-contact catenation strategy.”

The analysis is revealed within the journal Nature Chemistry.

This modern strategy makes use of hydrogen bonds, the cross-section of which could be seen as a “point,” relatively than the standard [π···π] stacking which entails giant “surface” overlap, to information catenation in a exact method in supramolecular crystals. Primarily based on this technique, researchers create a well-organized framework that minimizes floor loss brought on by interpenetration and tailors the pore diameter (~1.2–1.9 nm) for optimum hydrogen storage.

In consequence, the analysis workforce obtained a supramolecular crystal with record-high gravimetric (3,526 m2 g‒1) and balanced volumetric (1,855 m2 cm‒3) floor areas amongst all of the reported (supra)molecular crystals, along with excessive stability, whereas (i) bringing about wonderful material-level volumetric capability (53.7 g L‒1), (ii) balancing excessive gravimetric capability (9.3 wt%) for hydrogen storage beneath sensible strain and temperature swing circumstances (77 Okay/100 bar → 160 Okay/5 bar), and (iii) surpassing the DOE final system-level targets (50 g L‒1 and 6.5 wt%) each volumetrically and gravimetrically, albeit at cryogenic temperatures.

Progressive design

Designing natural supramolecular crystals that stability excessive gravimetric and volumetric floor areas, whereas additionally sustaining excessive stability, is a momentous problem, which has hindered its potential for a lot of purposes.

The workforce, nevertheless, has proposed a point-contact catenation technique that makes use of point-contact interactions involving hydrogen bonding to reduce floor loss throughout catenation. This design technique endows these supramolecular crystals with balanced excessive volumetric and gravimetric floor areas, excessive stability, and perfect pore sizes for hydrogen storage.

This analysis unlocks the potential of natural supramolecular crystals as promising candidates for onboard hydrogen storage and highlights the potential of a directional catenation technique in designing strong porous supplies for purposes.

Extra info:
Ruihua Zhang et al, Balancing volumetric and gravimetric capability for hydrogen in supramolecular crystals, Nature Chemistry (2024). DOI: 10.1038/s41557-024-01622-w

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The College of Hong Kong

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Natural supramolecular crystals with excessive hydrogen storage efficiency may improve fuel-cell car effectivity (2024, September 27)
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