4th April 2008

One of the key engineering challenges to building a clean, efficient, hydrogen-powered car is how to design the fuel tank. Storing enough raw hydrogen for a reasonable driving range would require either impractically high pressures for gaseous hydrogen or extremely low temperatures for liquid hydrogen. In a new paper* researchers at the National Institute of Standards and Technology’s Center for Neutron Research (NCNR) have demonstrated that a novel class of materials could enable a practical hydrogen fuel tank.

A research team from NIST, the University of Maryland and the California Institute of Technology studied metal-organic frameworks (MOFs). One of several classes of materials that can bind and release hydrogen under the right conditions, they have some distinct advantages over competitors. In principle they could be engineered so that refueling is as easy as pumping gas at a service station is today, and MOFs don’t require the high temperatures (110 to 500 C) some other materials need to release hydrogen.

In particular, the team examined MOF-74, a porous crystalline powder developed at the University of California at Los Angeles. MOF-74 resembles a series of tightly packed straws comprised of mostly carbon atoms with columns of zinc ions running down the inside walls. A gram of the stuff has about the same surface area as two basketball courts.

The researchers used neutron scattering and gas adsorption techniques to determine that at 77 K (-196 C), MOF-74 can adsorb more hydrogen than any unpressurized framework structure studied to date—packing the molecules in more densely than they would be if frozen in a block.

NCNR scientist Craig Brown says that, though his team doesn’t understand exactly what allows the hydrogen to bond in this fashion, they think the zinc center has some interesting properties.

“When we started doing experiments, we realized the metal interaction doesn’t just increase the temperature at which hydrogen can be stored, but it also increases the density above that in solid hydrogen,” Brown says. “This is absolutely the first time this has been encountered without having to use pressure.”

Although the liquid-nitrogen temperature of MOF-74 is not exactly temperate, it’s easier to reach than the temperature of solid hydrogen (-269 C), and one of the goals of this research is to achieve energy densities great enough to be as economical as gasoline at ambient, and thus less costly, temperatures. MOF-74 is a step forward in terms of understanding energy density, but there are other factors left to be dealt with that, once addressed, could further increase the temperature at which the fuel can be stored. Fully understanding the physics of the interaction might allow scientists to develop means for removing refrigeration or insulation, both of which are costly in terms of fuel economy, fuel production, or both.

Meanwhile, Scientists at U.S. Department of Energy’s Argonne National Laboratory are answering that call by working to chemically manipulate algae for production of the next generation of renewable fuels – hydrogen gas.

“We believe there is a fundamental advantage in looking at the production of hydrogen by photosynthesis as a renewable fuel,” senior chemist David Tiede said. “Right now, ethanol is being produced from corn, but generating ethanol from corn is a thermodynamically much more inefficient process.”

Some varieties of algae, a kind of unicellular plant, contain an enzyme called hydrogenase that can create small amounts of hydrogen gas. Tiede said many believe this is used by Nature as a way to get rid of excess reducing equivalents that are produced under high light conditions, but there is little benefit to the plant.

Tiede and his group are trying to find a way to take the part of the enzyme that creates the gas and introduce it into the photosynthesis process.

The result would be a large amount of hydrogen gas, possibly on par with the amount of oxygen created.

“Biology can do it, but it’s making it do it at 5-10 percent yield that’s the problem,” Tiede said. “What we would like to do is take that catalyst out of hydrogenase and put into the photosynthetic protein framework. We are fortunate to have Professor Thomas Rauchfuss as a collaborator from the University of Illinois at Champaign-Urbana who is an expert on the synthesis of hydrogenase active site mimics.”

Algae has several benefits over corn in fuel production. It can be grown in a closed system almost anywhere including deserts or even rooftops, and there is no competition for food or fertile soil. Algae is also easier to harvest because it has no roots or fruit and grows dispersed in water.

“If you have terrestrial plants like corn, you are restricted to where you could grow them,” Tiede said. “There is a problem now with biofuel crops competing with food crops because they are both using the same space. Algae provides an alternative, which can be grown in a closed photobioreactor analogous to a microbial fermentor that you could move any place.”

Tiede admitted the research is its beginning phases, but he is confident in his team and their research goals. The next step is to create a way to attach the catalytic enzyme to the molecule.

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