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US-China team develops new class of catalyst superior to platinum for H2O splitting and H2 generation

Master.img-002
Potential sweeps caused substantial activity degradation for the Pt catalyst, but nearly no activity change for the NiAu/Au catalyst. Credit: ACS, Lv et al.. Click to enlarge.

A team from Brown University, Wuhan University of Technology (China), Cal State University Northridge and Harbin Institute of Technology (China) has developed a new catalyst for a highly efficient hydrogen evolution reaction based on core/shell NiAu/Au nanoparticles (NPs).

In their paper, published in the Journal of the American Chemical Society, the researchers go on to suggest that their approach is not limited to NiAu but can be extended to FeAu and CoAu as well, providing a general approach to MAu/Au NPs as a class of new catalyst with platinum-like activity and much superior durability for water splitting and hydrogen generation.

Hydrogen evolution reaction (HER) is often referred to as electrochemical reduction of protons to hydrogen and is an important half reaction used to couple with oxygen evolution reaction in water splitting. It has been studied extensively as a sustainable way of producing H2 for clean energy applications. For HER to proceed smoothly without consuming extra energy, a catalyst must be present to initiate proton reduction with minimal overpotential.

Past studies have identified Pt-based catalysts as being the most effective in catalyzing HER due to their low reduction overpotentials and fast reduction kinetics in acidic media. To overcome the cost issues related to the Pt catalysts, recent efforts have been devoted to developing new catalysts from earth-abundant elements, such as Mo, W, and Ni and their molecular derivatives. Despite the promising catalysis demonstrated on HER, these catalysts are generally much inferior to the Pt-based ones with relatively high overpotentials. Consequently a new class of non-Pt catalysts with their catalysis superior to or comparable with Pt catalysts is still desperately needed before water splitting can be applied practically for hydrogen generation.

—Lv et al.

Other observations on the catalytic capability of gold, combined with recent studies on tuning electrocatalysis of core/shell structures for electrochemical reduction reactions, inspired the team to study core/shell M/Au NPs—where M is a first-row transition metal—as a non-Pt catalyst for HER.

During their work in synthesizing the catalysts, the researchers found that core/shell NiAu/Au NPs were more active for HER in an acid solution than either NiAu or Au NPs. They were nearly as active as the commercial Pt catalyst but with much enhanced durability.

The core/shell NiAu/Au has the Pt-like activity and is even more stable than the Pt in the HER condition, becoming the most efficient non-Pt catalyst ever reported for HER in acidic media. The first-principles calculations suggest that the high activity of core/shell structure arises from the formation of the Au sites with low coordination numbers. Analyses on the Tafel slopes reveal that the defected Au shell in the NiAu/Au structure facilitates the recombination of two adsorbed H atoms and therefore the HER. Our study provides a general approach to MAu alloy and MAu/ Au core/shell NPs for catalytic tuning and optimization. The optimized MAu/Au can replace Pt to catalyze HER for important energy applications.

—Lv et al.

Resources

  • Haifeng Lv, Zheng Xi, Zhengzheng Chen, Shaojun Guo, Yongsheng Yu, Wenlei Zhu, Qing Li, Xu Zhang, Mu Pan, Gang Lu, Shichun Mu, and Shouheng Sun (2015) “A New Core/Shell NiAu/Au Nanoparticle Catalyst with Pt-like Activity for Hydrogen Evolution Reaction” Journal of the American Chemical Society doi: 10.1021/jacs.5b01100

Comments

mahonj

Looks like good news: renewable h2 without platinum.

Now, we have to find something to do with the h2: store it (tricky) or react it with some carbon (coal or biomass) to make a more valuable liquid HC fuel.

Davemart

The very fast progress in many technologies for the economic and efficient production and use of hydrogen should lead those who opposed it to reconsider, if their purported grounds for the opposition were in fact the underlying cause.

Here is betting that very few of those so opposed will modify their position at all.

Engineer-Poet

Taking your bait... this catalyst solves (sort of) the problem of capital cost in the electrolyzer's catalyst.  It still leaves the other 4 required miracles wanting, not the least the cost of the energy (electric) required to drive it.

Davemart

Hi EP:
As always I was not really thinking of you in my strictures against opponents of hydrogen and fuel cells, as I in any case just like you would much prefer if we just got on with it and built nuclear which would most efficiently power BEVs.

But they ain't, and the only way I can see of squaring the circle of low carbon without is to use a heck of a lot of hydrogen and its derivatives.

As for the points you raise:

Lower the production cost of fuel cell cars - already happening, and fast.
The Mirai etc are only small trial runs.

Enough hydrogen in the car for decent autonomy - the present generation carries enough for around 265 miles or so.
It is a lot easier on bigger cars to carry more hydrogen, but Toyota have already hit the DOE target of hydrogen by weight for 2020, and further progress giving around another 20% seems perfectly possible.
It is early days, but once the technology is more established either on board reforming or high temperature cells using a variety of fuels may become possible.

Solve the production cost of hydrogen - we are doing pretty good, as this article and umpteen others on this blog show for a variety of technologies.

Build the fuelling infrastructure - it is happening, when opponents said it wouldn't.
Here is Germany:
http://cleanenergypartnership.de/fileadmin/Assets/user_upload/50_TS.pdf
That gives them sketchy coverage of the whole country.

Hope competitive technologies don't improve - eg hybrid cars

FCEVs work just fine as a plug in hybrid, as Audi intend.

electric-car-insider.com

The prospect of an FCEV plug on hybrid might seem appealing but the reason no one is building them at this point is that you the get the worst of both worlds in a couple of ways.

An expensive h2 power plant and storage system on board, with the need for a larger(er) more expensive battery.

More complexity, much more difficult packaging issues. Take a look at the Mirai cut-away Toyota shows at auto expos and tell me where you would stuff a Volt-sized battery.

If people only have to re-fuel with liquid fuels very infrequently, that hydrogen infrastructure ROI looks even less attractive as an investment. And it's already un-economic.

Given the increased cost, for both car and fprefueling infrastructure, I don't see how a FCEV wins in the marketplace against a Volt-style PHEV which gets 50 miles all-electric range, but can still take you to grandmas on a moments notice, and has no performance limitations.

It won't be winning on cost any time in the forseeable future.


Davemart

The reason that they are not building PHEV FCEVs at the moment is that you build the simplest design first and that tells us nothing about what configuration will be preferred later.

It is odd that those who are keen on getting off petrol suddenly get sentimental about it and want to go for PHEV ICE instead of fuel cells if they can't have their preference of nothing but batteries.

A fuel cell combines far better than an ICE with batteries.
And it still produces zero pollution at point of use and uses no oil, which were supposed to be the two great advantages of electrification.

If hydrogen is very cheap, and there seem to be several ways this might happen, then they won't bother much with plug ins.

If hydrogen is more expensive, than a plug in knocks out the already dubious proposition that they would be too expensive to fuel.

With anything like current batteries BEVs with really decent range won't be winning on cost any time in the forseeable future.

electric-car-insider.com

DM> If hydrogen is very cheap...

I agree that if someone developed a way to create cheap, renewable, low carbon hydrogen, that would be an important step forward. But there would still be a cheap infrastructure to build, cheap on board storage to solve, cheap fuel cells to build. That's a lot of "ifs".

With batteries on a long term downward trend of 8% per year, BEVs get competitive with ICEs capital cost within 10 years (ICE costs are going up).

A $35k, 200 mile Chevy Bolt, Tesla Model 3 or Nissan Leaf will be cost competitive on a TCO basis within 5 years, by 2020.

I'm not sentimental about fossil fuels in the least, but recognize that a PHEV that could deliver 80% of its lifetime service as an electric would achieve almost 80% of the cost and environmental savings of a BEV and be universally appealing no matter what the state of your local EV charging infrastructure.

If OEMs can deliver this "go anywhere" capability for a premium of only ~3k over a current ICE, payback is about 2 years. That leaves another 10 years of very low cost, low environmental driving without having to build a trillion dollar hydrogen refueling infrastructure.

Davemart

If we are in the business of predicting the future, over the same kind of time we have the DOE predicting $30kw fuel cells, without the breakthroughs needed for much higher density batteries.

The stuff about how unaffordable building hydrogen stations are is simply nonsense.

The same folk were confidently saying that the roll out we have already seen would not happen.

In Europe we already have 3 systems in use, petrol and diesel universal, and NG which is also a high pressure gas and uses much of the same equipment as hydrogen in extensive supply, with for instance 900 stations in Germany alone.

The German's put the cost of rolling out hydrogen stations at around the same level as the NG stations.

So those with the most experience of alternative fuelling infrastructures see the problem as perfectly manageable.

Davemart

I should add that it is way, way tougher to wire up all the places where cars are kept beside the road than to provide hydrogen at 10-15% of petrol stations.

Engineer-Poet

CNG has roughly 3x the energy density of H2 at the same pressure, and much better than that as liquid.

I'm agnostic on the issue of hydrogen per se.  You can get 17 wt% storage by using ammonia; the sodium-amide process converts it to gases at a small energy cost.  Burn it in an engine until the FC makes it, fine; $30/kW has been a fait accompli for years.  What gets me is the upstream end, where un-sequestered NG and even gasified coal will have a large cost advantage over anything electrolytic.  That is what we have to get rid of, preferably by eliminating its market.  HFCs don't do that.

Davemart

EP:

There have been very large cost reductions in just about everything to do with hydrogen, including electrolysis.

To say that if pollution is ignored then unsequestered coal etc has the cost advantage is simply the same as for energy production in general, as we would be burning far more coal if mandates etc did not reduce it.

A fuel cell cycle even on existing coal and natural gas plants can clean up their emissions a lot, and enable cheaper capturing of a purer stream of CO2, whilst simply using fuel cells almost eliminates NOx and brings sequestration into sight at some reasonable cost.

They can't do the almost complete job that nuclear can, but fuel cells can enormously reduce GHG emissions,

mahonj

@ECI
"I'm not sentimental about fossil fuels in the least, but recognize that a PHEV that could deliver 80% of its lifetime service as an electric would achieve almost 80% of the cost and environmental savings of a BEV and be universally appealing no matter what the state of your local EV charging infrastructure."

Very nicely put - you can size a PHEV battery for your average drive rather than the longest you would undertake.
Thus, you can get away with 5,10,15 KwH rather than 25kwh as a starting bid.

However, you do need two engines and this increases the cost and complexity.
What is needed is a good range extender generator (not like the one in the BMW I3). [You could run it off CNG if you liked, but diesel or gasoline would do fine. ]

Peterww

Ignoring all the debate above over FCEVs Vs BEVs, and returning to the news item, I am astonished that nobody here remarked that the substitute for Platinum mentioned there involves a metal known as Au, or Gold in everyday terms. Not at all an earth abundant element, so I do not see great progress in this.

Engineer-Poet

Good point.  Gold is about 1/3 as abundant as Pt, so unless the alloy nanoparticles are far more economical with it then this is pretty much a nothingburger.

Davemart

I was hoping that the design was by Doc Emmett Brown, so that if you ran out of fuel you could simply chuck in your Rolex! :-)

mahonj

@EP, @Peterww, from the same wikipedia link EP posted, the world produces 2700 tons of gold / year and 179 tons of platinum.
From this measure, gold is about 15 times more available than Pt.

Davemart

mahonj:
Good post.
We also don't know how much gold is needed, and presumably since they are bothering developing it they see the costs as acceptable.

gorr

Invent a way to produce hydrogen for free and make gasoline with it at a better cost than actual petroleum gasoline.

JMartin

I am surprised no one bothered to look at the current prices. Gold and platinum are selling at about the same price right now -- Gold $1193, and Platinum $1139. So I guess the real issue is how much is used.

Roger Pham

@Peterww,
Good point about the high cost of Gold, but the gist of this article is: "... They were nearly as active as the commercial Pt catalyst but with much enhanced durability.
This would mean perhaps reduction in operation cost of electrolyzers due to longer intervals between maintenance or replacement.

All the golds in Fort Knox are sitting there, doing nothing. Now there is a way for uncle Sam to actually do something productive with all that gold, an investment that keeps on giving us stored Renewable Energy for home use, industry, transportation...until the end of time!

HarveyD

Platinum (Pt) and Gold (AU) are both too rare and too costly to be used in low cost electrolizers and/or low cost fuel cells, except when combined with other very cost elements.

The Earth crust contains about 25% more Platinum than Gold but 15 times more Gold is mined. The commercial price is almost the same.

Many more much lower cost catalysts will soon be developed.

Bob Wallace

Compressed hydrogen holds about 10% as much energy as gasoline per volume.

Wiki says that fuel cells run about 40% efficient with Honda claiming a 60% efficient fuel cell. ICEs run about 20%. (Rough numbers here.)

With 40% efficiency a FCEV would be about twice as efficient as a ICEV. With 60% efficiency the FCEV would be about three times as efficient. Either way that means that a lot more hdrogen volume is going to have to be moved and stored compared to gas/diesel. As much as five times more.

That means a lot more space to store H2 compared to the underground tanks now used for gasoline. And it means as much as five times more railroad tankers and fuel trucks to move the volume.

AmIright?

Furthermore with a 300 mile range as opposed to a 400 to 500 mile range for ICEVs we'd need more fueling stations. At 300 vs. 400 we'd need to increase the number of pumps by 25% over what we now use.

Starting with a 10x disadvantage wouldn't that mean it would take

HarveyD

An extended range PHEV-FC equipped with 1/3 the battery pack of an extended range equivalent BEV could run 80%to 90%% of the time on electricity from the grid or from home solar system. The FC range extender would be used for the remainder (10% to 20% max for occasional long trips).

Very few H2 stations (mainly on highways) would be required for very large PHEV-FC fleets.

Many areas and countries have temporary clean e-energy excess/surpluses, specially during off-peak demand hours (16 to 18 hours/day). Most of this excess/surplus e-energy could be used to produce and store lower cost H2. Some of the stored H2 could be used to produce e-energy with large FCs during peak demand hours.

Bob Wallace

PHEVs using fuel cells would work, but they may lose out based on cost.

With a 1/3rd as large battery pack the battery pack is going to get heavy use and will need to be replaced 3x or more compared to the larger EV pack. Most days the EV pack will be mildly discharged while the PHEV pack will endure a deep discharge.

The fuel cell and tanks may well cost more than extra batteries.

And H2 for the longer trips will certainly be more expensive than charging up once or twice.

The extra/surplus electricity can as easily be used to charge EV batteries and would turn into 2x to 3x more miles driven.

The only hope I can see for fuel cell cars is for fuel cells to get very cheap, very fast and for someone to figure out how to make the cost of H2 per mile the same or less than electricity. That's a double difficult task.

HarveyD

@BW..it all depends were you live and what is your driving pattern.

In our area we have an ongoing surplus of very low cost clean e-energy and cold long winters.

Extended range (600+ KM) BEVs would need 120+ kWh quick charge battery pack to satisfy our driving needs and keep the cabin warm during our long cold seasons.

PHEV-FC with 30 to 40 kWh battery pack and a small 20-25 KW FC could supply the extended range (600+ KM) needed while keeping the cabin in the comfort zone.

Such a vehicle would operate on very low cost clean e-energy only 80% to 90% of the time without discharging more than 80% level.

Many current battery technologies can already sustain slow recharges 5 times/week during 102 to 18 years.

It is doable, for a few dollars more, than PHEVs with polluting ICE range extender.

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