Making clean hydrogen is hard, but researchers just solved a major hurdle

UNIVERSITY OF TEXAS AT AUSTIN

IMAGE
IMAGE: THE TEAM’S EXPERIMENTAL WATER-SPLITTING APPARATUS. view more 
CREDIT: COCKRELL SCHOOL OF ENGINEERING, THE UNIVERSITY OF TEXAS AT AUSTIN

For decades, researchers around the world have searched for ways to use solar power to generate the key reaction for producing hydrogen as a clean energy source — splitting water molecules to form hydrogen and oxygen. However, such efforts have mostly failed because doing it well was too costly, and trying to do it at a low cost led to poor performance.

Now, researchers from The University of Texas at Austin have found a low-cost way to solve one half of the equation, using sunlight to efficiently split off oxygen molecules from water. The finding, published recently in Nature Communications, represents a step forward toward greater adoption of hydrogen as a key part of our energy infrastructure.

As early as the 1970s, researchers were investigating the possibility of using solar energy to generate hydrogen. But the inability to find materials with the combination of properties needed for a device that can perform the key chemical reactions efficiently has kept it from becoming a mainstream method.

“You need materials that are good at absorbing sunlight and, at the same time, don’t degrade while the water-splitting reactions take place,” said Edward Yu, a professor in the Cockrell School’s Department of Electrical and Computer Engineering. “It turns out materials that are good at absorbing sunlight tend to be unstable under the conditions required for the water-splitting reaction, while the materials that are stable tend to be poor absorbers of sunlight. These conflicting requirements drive you toward a seemingly inevitable tradeoff, but by combining multiple materials — one that efficiently absorbs sunlight, such as silicon, and another that provides good stability, such as silicon dioxide — into a single device, this conflict can be resolved.”

However, this creates another challenge — the electrons and holes created by absorption of sunlight in silicon must be able to move easily across the silicon dioxide layer. This usually requires the silicon dioxide layer to be no more than a few nanometers, which reduces its effectiveness in protecting the silicon absorber from degradation.

The key to this breakthrough came through a method of creating electrically conductive paths through a thick silicon dioxide layer that can be performed at low cost and scaled to high manufacturing volumes. To get there, Yu and his team used a technique first deployed in the manufacturing of semiconductor electronic chips. By coating the silicon dioxide layer with a thin film of aluminum and then heating the entire structure, arrays of nanoscale “spikes” of aluminum that completely bridge the silicon dioxide layer are formed. These can then easily be replaced by nickel or other materials that help catalyze the water-splitting reactions.

When illuminated by sunlight, the devices can efficiently oxidize water to form oxygen molecules while also generating hydrogen at a separate electrode and exhibit outstanding stability under extended operation. Because the techniques employed to create these devices are commonly used in manufacturing of semiconductor electronics, they should be easy to scale for mass production.

The team has filed a provisional patent application to commercialize the technology.

Improving the way hydrogen is generated is key to its emergence as a viable fuel source. Most hydrogen production today occurs through heating steam and methane, but that relies heavily on fossil fuels and produces carbon emissions.

There is a push toward “green hydrogen” which uses more environmentally friendly methods to generate hydrogen. And simplifying the water-splitting reaction is a key part of that effort.

Hydrogen has potential to become an important renewable resource with some unique qualities. It already has a major role in significant industrial processes, and it is starting to show up in the automotive industry. Fuel cell batteries look promising in long-haul trucking, and hydrogen technology could be a boon to energy storage, with the ability to store excess wind and solar energy produced when conditions are ripe for them.

Going forward, the team will work to improve the efficiency of the oxygen portion of water-splitting by increasing the reaction rate. The researchers’ next major challenge is then to move on to the other half of the equation.

“We were able to address the oxygen side of the reaction first, which is the more challenging part, ” Yu said, “but you need to perform both the hydrogen and oxygen evolution reactions to completely split the water molecules, so that’s why our next step is to look at applying these ideas to make devices for the hydrogen portion of the reaction.”

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This research was funded by the U.S. National Science Foundation through the Directorate for Engineering and the Materials Research Science and Engineering Centers (MRSEC) program. Yu worked on the project with UT Austin students Soonil Lee and Alex De Palma, along with Li Ji, a professor at Fudan University in China.

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July 20, 2021 8:11 am

I’ve read many articles on “green” hydrogen. All of them seem to ignore hydrogen storage, as if there were no issues with storing hydrogen. Hydrogen can be stored at high pressure, as a liquid (20 K), by chemical conversion or physical adsorption. All of these methods require energy.
They also ignore the safety issues of hydrogen. Tom Johnson’s explanation of the problems of piping gaseous hydrogen is spot on.

If hydrogen leaks, it has an explosive range of 4% to 90% in air. This is far wider than any common fuel gas or vaporized liquid. The energy of ignition is very low for a H2/air mixture. When hydrogen burns it does radiate heat like most other fires. A hydrogen flame burns with a very pale blue flame. In daylight, you can’t see a hydrogen flame, although you can often see heat strirations above the flame. This means that you can walk into a hydrogen flame and not realize it until you feel the pain.

Dudley Horscroft
Reply to  Brooks H Hurd
July 20, 2021 9:09 am

Howard Hughes’s steam propelled car comes to mind. The story is that the engineers produced a prototype, and it ran well, and they demonstrated it to Hughes. He wondered – “traffic accident safety” and took a axe and hit a car door with it. The engineers had used the doors as part of the cooling circuit to save water, rather than exhausting the used steam to air. The blast of high pressure steam from the door convinced Hughes it was a no goer and the project was scrapped.
So will any large scale hydrogen project.

JamesD
July 20, 2021 9:01 am

Just use solar cells and electrolysis. Not that that makes sense as a fossil fuel replacement as you still have to compress the hydrogen, however gut feel is that it would be more efficient.

July 20, 2021 9:05 am

Why go to all the trouble to produce hydrogen to burn when you can more efficiently burn natural gas. When you burn natural gas you are burning four hydrogen atoms for each carbon atom.

Reply to  Fred Haynie
July 20, 2021 8:34 pm

Hush. Its not “Carbon Free” then.

Don’t forget, we used to want to reduce carbon dioxide to 1990 levels by 2030, but somewhere along the line in the last few years environmentalists changed this to 6000 BC levels by 2050.

No one ever blinked or said Huh? once. Go figure.

Steve Z
July 20, 2021 9:09 am

If the researchers are trying to use sunlight to run a “water-splitting” reaction, there needs to be some mechanism to collect the hydrogen, and keep it separate from the atmosphere. Any oxygen molecules produced can be simply released into the atmosphere.

It’s not clear why the researchers talk about the “oxygen part” and the “hydrogen part” of the reaction–if two water molecules are split, they produce one molecule of O2 and two molecules of H2, so there needs to be some mechanism for collecting the hydrogen molecules and keeping them separate from the atmosphere. The surface holding the water would have to be transparent (to allow sunlight in) while preventing evaporation of water.

As many commenters below have correctly noted, hydrogen is difficult to contain in a pipeline or even a stationary tank, and tends to corrode any metal with which it comes into contact.

Hydrogen has a heat of combustion of about 57.8 kcal/mole, as compared to 191.8 kcal/mole for methane, the majority compound in natural gas. At a given temperature and pressure, the volume of a gas is proportional to the number of moles, so that burning a given volume of methane delivers 3.32 times as much energy as the same volume of hydrogen. Put another way, to store the same amount of energy as hydrogen requires a tank at 3.32 times the pressure of a tank of methane, for the same volume. This means that hydrogen tanks have to have thicker walls to resist the pressure, and be made of more exotic metals to resist corrosion, while methane pipelines can usually be made of relatively cheap carbon steel.

It is true that highly purified hydrogen is used extensively in petroleum refineries, and they have installed the necessary materials for safely handling hydrogen. However, in a petroleum refinery the goal is to use hydrogen as a reactant in desulfurization reactions with distillate oils (kerosene, diesel, gasoils, etc.), and only a small fraction of the hydrogen produced is actually burned.

Hydrogen is a highly reactive gas, and this reactivity is useful in many applications, including petroleum refining and manufacture of fertilizers. However, as a fuel, hydrogen has a relatively low energy density (energy release per unit volume), so that high pressures and exotic metals are needed to store and transport it.

Jeff Corbin
July 20, 2021 9:31 am

Does anyone know anything about the use of 3D graphene as high-capacity sorbents for safe hydrogen storage?

Rich Davis
July 20, 2021 10:00 am

Oxidizing water? Another YouReekAlot! gem. Their writers are dumber than a box of rocks.

Maybe they’re talking about the burning Cuyahoga river?

https://www.smithsonianmag.com/history/cuyahoga-river-caught-fire-least-dozen-times-no-one-cared-until-1969-180972444/

Bruce Cobb
July 20, 2021 1:04 pm

Cleaning hydrogen is easy with our safe, effective and easy-to-use HYDROKLEEN™ System. Call now: 1-800-H2KLEEN. Operators are standing by.

Ferdberple
July 20, 2021 1:54 pm

efficiently oxidize water.
=======
Technically they are reducing water. Oxidizing water yields hydrogen peroxide.

James
July 20, 2021 7:00 pm

Surely the elephant in the room is the emissions? We have been told for years that water vapour is a much worse greenhouse gas than CO2. But now we have “green” hydrogen that produces water vapour when burned, this fact is conveniently ignored. Or am I missing something?

Tom
Reply to  James
July 21, 2021 8:14 am

Yes, you are missing a couple of things. First, the air typically contains as much as 10 times as much water vapor as carbon dioxide. At 20 deg C and 50% relative humidity, the air will contain about 8 gms of water/Kg of dry air. This amounts to about 8000 ppmw or 12,300 ppmv. Carbon dioxide in the atmosphere is well mixed and stays in the atmosphere for a long time. Water vapor is not well mixed. The water in air changes a lot with temperature and altitude. When wet air rises and cools, the water vapor condenses out and falls as rain, snow, or ice. The second thing is that since there is so much water vapor in the air, the effect on atmospheric water vapor due to combustion would be very small, in addition to the factors previously mentioned. Warm air will hold more water vapor than cold air, and water will evaporate faster at higher temperatures, so, in theory, a warming planet will also have a generally wetter atmosphere, which should result in more rainfall, in theory.

John M
July 20, 2021 7:43 pm

Oxidizing water is indeed the term used.

https://en.wikipedia.org/wiki/Heterogeneous_water_oxidation

More to the point, I have no idea what the good perfessor is talking about with regard to improving the hydrogen formation half of the reaction. The underlying paper clearly states the experiment makes both gases, so I guess we’ll have to make allowances for trying to simplify things for the press room.

I suspect this is a nice elegant piece of scientific work that’s a long way from being commercial.

As James Van Allen purportedly said when asked about the usefulness of his discovery of the Van Allen Belts: “Well, I’m making a pretty good living off of them.”

July 20, 2021 9:29 pm

I note in one of the three “Related” articles

[https://wattsupwiththat.com/2014/07/14/the-law-of-unintended-consequences-in-action-imagine-replacing-all-co2-emissions-with-h2o-emissions/?]

the photograph of a gentleman filling a glass with the exhaust product of a hydrogen fueled vehicle, water.

Great, if pure oxygen is used. But what about using ‘air’ – we will still be getting various oxides of nitrogen. A hotter or cooler ‘burn’ compared to gasoline – a different mixture of nitrogen oxides? Would/could nitrous oxide be one of the components? (Laughing gas)

pochas94
July 21, 2021 9:26 am

I’m betting you could make ‘dirty’ hydrogen this way, too.