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Highlights in Chemical Science

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Borane leads the way to alternative fuels


02 July 2008

New routes to hydrogen storage materials, which could offer alternative fuel for cars, have been developed by two teams of scientists in the US and Singapore.

Hydrogen is an important energy source as it reacts with oxygen to release energy with the only by-product being water. However, at atmospheric pressure it is gaseous, and therefore needs to be stored at high pressure to reduce the storage volume.  By using a solid material with a high hydrogen content, the volume required for hydrogen storage is considerably reduced, and the need for high pressure eliminated.

 

car tyres with ammonia borane axle

Ammonia borane could provide a source of hydrogen for fuelling the cars of the future

 

Ammonia borane (NH3BH3) has a high hydrogen content and is stable at room temperature, but has, in the past, proven difficult to prepare in high yield. Now, Tom Autrey and co-workers at the Pacific Northwest National Laboratory, Richland, US, have developed a new one-pot synthetic method to this solid material.1

Autrey's method requires in situ production of ammonium borohydride (NH4BH4) by the addition of NH4X and MBH4 salts (X = Cl, F, M = Na, Li) in liquid ammonia, followed by removal of the majority of the ammonia, then addition of tetrahydrofuran (THF) which causes the NH4BH4 to decompose to ammonia borane in high yield.

"The long-term challenge is to regenerate ammonia borane from the spent storage material"
- Tom Autrey
As Autrey explains, 'to be a viable hydrogen storage material economic routes to synthesis and regeneration are of the utmost importance'. At the moment hydrogen release from ammonia borane is not reversible, therefore Autrey says the 'long-term challenge is to regenerate ammonia borane from the spent storage material'.

Another problem with ammonia borane is that its decomposition leads to the production of the volatile compound borazine as a by-product. Borazine can poison proton exchange membrane fuel cells. This issue has been addressed by another team, led by Ping Chen at the National University of Singapore.2

"This work opens the road to new materials for storing hydrogen"
- Zhitao Xiong
Chen proposes the use of sodium aminoborane (NaNH2BH3) as an alternative to ammonia borane as it does not release borazine on decomposition.  Traditionally sodium aminoborane is made using a mechano-synthetic route which requires additives to aid milling. But these additives cause a reduction in the hydrogen density of the product.

Chen's wet-chemical method allows pure sodium aminoborane to be made. He proposes two routes, the faster of which involves adding sodium hydride (NaH) to a solution of ammonia borane (NH3BH3) in THF. The reaction occurs within 10 minutes at -3 C, giving solid sodium aminoborane which can be filtered off.

Zhitao Xiong, a member of Chen's team, says the most important aspect of this work is that 'it opened the road to a new class of materials comprising alkali or alkaline earth metal cation and [NH2BH3]- anion for storing hydrogen'.

"A major effort to develop economical methods for regeneration of ammonia borane is required if such materials are to be used as hydrogen sources for automobiles"
- Todd Marder
Todd Marder at Durham University, UK, welcomes both teams' research, saying 'the study of materials which can store and release, under mild conditions, a significant percentage of their weight as hydrogen, is certainly one which is of considerable importance. However, given that the hydrogen release is not reversible, a major effort to develop economical methods for regeneration of ammonia borane is required if such materials are to result in commercially viable technologies for common use as hydrogen sources for automobiles.'

Vikki Chapman

References

1.  David J. Heldebrant, Abhi Karkamkar, John C. Linehan and Tom Autrey, Energy Environ. Sci., 2008, DOI: 10.1039/b808865a

2.  Zhitao Xiong, Guotao Wu, Yong Shen Chua, Jianjiang Hu, Teng He, Weiliang Xu, Ping Chen, Energy Environ. Sci., 2008, DOI: 10.1039/b805649h

Link to journal article

Synthesis of ammonia borane for hydrogen storage applications
David J. Heldebrant, Abhi Karkamkar, John C. Linehan and Tom Autrey,Energy Environ. Sci., 2008, 1, 156
DOI: 10.1039/b808865a

Synthesis of sodium amidoborane (NaNH2BH3) for hydrogen production
Zhitao Xiong, Guotao Wu, Yong Shen Chua, Jianjiang Hu, Teng He, Weiliang Xu and Ping Chen,Energy Environ. Sci., 2008, 1, 360
DOI: 10.1039/b805649h

Also of interest

The holey grail of hydrogen storage

A polymer riddled with tiny pores could lead to a novel hydrogen fuel tank, say chemists in the US

Ironing out fuel cells

A simple iron complex could pave the way for new oxygen reduction catalysts with potential uses in low-temperature fuel cells

Hydrogen storage in liquid organic heterocycles
Robert H. Crabtree,Energy Environ. Sci., 2008, 1, 134
DOI: 10.1039/b805644g