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China team develops highly efficient catalyst for low-temperature aqueous phase refoming of methanol to produce hydrogen

1 April 2017

Researchers in China, along with colleagues in the US, have developed a new catalyst that shows outstanding hydrogen-production activity and stability in the low-temperature aqueous phase reforming of methanol (APRM).

In a paper in the journal Nature, the team reports that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150–190 ˚C), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. The new catalyst, the researchers suggest, paves a way towards a commercially achievable hydrogen-storage strategy.

Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight.

But traditional reforming of methanol steam operates at relatively high temperatures (200–350 degrees Celsius), so the focus for vehicle and portable PEMFC applications has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks. There remains, however, the need for an efficient APRM catalyst.

—Lin et al.

Earlier work has suggested that to achieve a high rate of hydrogen production from the reaction of methanol and water at low temperatures, both the water and the methanol must be activated effectively. This, the team said, can be difficult to achieve with a homogeneous catalyst that contains only isolated noble-metal sites; as a result, they reasoned that a bifunctional structure might be important.

A suitable material would not only act as a support for confined metal atoms, but would also modulate their electronic structure.

Because the electronic structure of metal catalysts can be tuned by their supports or promoters, and because electron-deficient platinum nanoparticles have been proposed to be responsible for the high activity of the low-temperature water–gas shift reaction1, careful choice of the support material for platinum should in principle make it possible to obtain bifunctional constructs with atomically dispersed noble-metal sites that catalyse low-temperature APRM.

—Lin et al.

The research team had earlier found that α-MoC exhibits stronger interactions with platinum than do common oxide supports or β-Mo2C. The strong interactions drive an atomic dispersion of platinum (Pt1) over α-MoC during a high-temperature activation process. This results in an exceptionally high density of electron-deficient surface Pt1 sites for the adsorption/activation of methanol.

The α-MoC substrate shows high water-dissociation activity, producing abundant surface hydroxyls that accelerate the reforming of reaction intermediates at the interface between platinum and α -MoC. These two effects combine to confer the platinum/α-MoC catalyst with its very high catalytic and good stability in the base-free APRM process at 150–190 °C.

China is the global leader in methanol use and has recently expanded its methanol production capacity. A study commissioned by the US Energy Information Administration (EIA) recently found that since the early 2000s, China’s consumption of methanol in fuel products has risen sharply. The report estimates consumption to have been more than 500,000 barrels per day (b/d) in 2016.

Resources

  • Lili Lin, Wu Zhou, Rui Gao, Siyu Yao, Xiao Zhang, Wenqian Xu, Shijian Zheng, Zheng Jiang, Qiaolin Yu, Yong-Wang Li, Chuan Shi, Xiao-Dong Wen & Ding Ma (2017) “Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts” Nature doi: 10.1038/nature21672

April 1, 2017 in Catalysts, Hydrogen Production, Methanol | Permalink | Comments (18)

Comments

We can reform methanol to hydrogen on vehicle for PEM fuel cells.

It take more then 10 years before even choosing what they will do and even after 10 years they choose the wrong decision. We will never have this methanol invention, even if it's good actually. So i deeply recommend to all folks to protest about all these inneficients cars and energy market by spending the least amount of money possible, and let them go bankrupt.

This process operates at about 400 degrees F; That proves the downside of reforming carbon gasses to hydrogen; you lose far more energy breaking the hydrogen bonds than you will ever recover. And, then you use the H2 in a 40% efficient fuel cell...throwing away 60% of the hydrogen...makes no sense at all. But nothing has changed; the whole 120 year old process of using oil from the well to wheels is only efficient in the gross amount of pollutes it creates.

Efficiency is now the name of the game in the energy sector which will leave oil completely out of the fuel game except as a feedstock for petrochemicals and tires.

No sense at all...
Refineries "throw away" 20% then the engine wastes 70%.
You have 30% with methanol/H2/FC or 20% with oil to ICE.
NOW you have no NOx nor other smog creating pollution PLUS you can make renewable methanol.

There are more uses for this than powering vehicles. One use is to heat and provide electricity for homes. Some of the hydrogen produced goes to heat the process to generate more, with the heat as a byproduct. Certainly of more interest in cold countries.
gorr, if you want to be a better Russian denier you will have to learn to tone down you extreme denial.

Hi SJC.

Apparently this method would actually take place within the fuel stack:

' This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks'

Lad:

PEM fuel cells run at an average actual efficiency in cars of around 50%, not 40%.

At least get your prejudiced claims in the right area.

Creating and storing hydrogen from electrolysis using surplus electricity from wind and solar makes sense to do after you fill up the storage batteries.

An electric airliner using ducted electric fans and fuel cells would be a good use for hydrogen...no smog, just water, perhaps in the future.

It just uses catalysts that lower the reaction temperature whether done in or outside the stack. Since PEMs evolved as they are, doing this outside makes sense.
The same amount of energy is lost whether oil to wheels or methanol to wheels but we can make the renewable methanol while not getting the pollution nor fossil carbon.

I don't think this one has come up here, so I will mention it:

'The diagram shows the technology developed at the Technion: the oxygen and hydrogen are produced and stored in completely separate cells. According to Ms. Landman, one of the electrodes (anode) can be replaced by a light sensitive electrode (photo-anode), so that the conversion of water and solar energy into hydrogen fuel and oxygen will be carried out directly in each compartment simultaneously. Image Credit: American Technion Society. Click image for the largest view.
The new process allows geographic separation between the solar farm consisting of millions of PEC cells that produce oxygen exclusively, and the site where the hydrogen is produced in a centralized, cost-effective and efficient manner. They accomplished this with a pair of auxiliary electrodes made of nickel hydroxide, an inexpensive material used in rechargeable batteries, and a metal wire connecting them.
Avigail Landman, a doctoral student in the Nancy & Stephen Grand Technion Energy Program explained, “In the present article, ‘Photoelectrochemical Water Splitting In Separate Oxygen and Hydrogen Cells’ published in Nature Materials, we describe a new method for producing hydrogen through the physical separation of hydrogen production and oxygen production. According to our cost estimate, our method could successfully compete with existing water splitting methods and serve as a cheap and safe platform for the production of hydrogen.”
This is not the whole of the technology, as noted previously, the vision of the Technion researchers is geographic separation between the sites where the oxygen and hydrogen are produced: at one site, there will be a solar farm that will collect the sun’s energy and produce oxygen, while hydrogen is produced in a centralized manner at another site, miles away.
Thus, instead of transporting compressed hydrogen from the production site to the sales point, it will only be necessary to swap the auxiliary electrodes between the two sites. Economic calculations performed in collaboration with research fellows from Evonik Creavis GmbH and the Institute of Solar Research at the German Aerospace Center, indicate the potential for significant savings in the setup and operating costs of hydrogen production.'
http://newenergyandfuel.com/http:/newenergyandfuel/com/2017/03/22/separate-cells-for-hydrogen-and-oxygen-in-water-splitting/

I have become convinced over the last couple of years that fuel cell technology is going to play a very major part one way or another in our energy future, and that those who have sought to dismiss them as 'fool cells' have proven themselves to be the fools.

Elsewhere I see that Stephen Loveday is busy inventing facts on fuel cell cars:

'The Prime gets a major range upgrade, and the company is promoting the vehicle more heavily (now that it has set aside focus on the fuel-cell market, due to mounting expense and lack of charging infrastructure).'
http://insideevs.com/toyota-chairman-new-generation-plug-in-hybrids/

Nowhere is it made clear that that is his interpretation, based on neither Toyota statements nor the Reuters source for his article.

What is true is that Mercedes is de-emphasising fuel cell cars, not Toyota.

I would have thought that it would e better to leave methanol as methanol and burn it directly in a generator or engine.
At least methanol is a liquid and easy to store / transport, not like H2.

Hi Mahonj.

Unfortunately the figures I have found are all a bit arm-wavy instead of giving precise data:

'They also claim that a car with a 50 liter tank of methanol and just six to 10 grams of their catalyst could power a Toyota Mirai for approximately 690 km. Also, it would cost just $15 for the methanol and $320 for the platinum, which the team suggests, might be recyclable.'

https://phys.org/news/2017-03-platinum-molybdenum-carbide-catalytically-hydrogen-power.html#jCp

Without the rating cycle used for the Mirai range etc there is no way of telling what that means.

At least the fuel cell would not presumably be emitting the formaldehyde combusting it does, in an otherwise very clean burning fuel:
https://www.google.co.uk/search?as_q=methanol+combustion+emissions&as_epq=&as_oq=&as_eq=&as_nlo=&as_nhi=&lr=&cr=&as_qdr=all&as_sitesearch=&as_occt=any&safe=images&as_filetype=&as_rights=

I'd see the likely application of this though more in RE's, where methanol would be a very good fuel for a small 30 KW or so RE on a PHEV.

While Methanol can definitely be used as a transportation fuel directly. In most cases today it is not Carbon Neutral (produced using Coal in China or from Natural Gas, and in the FC or ICE vehicle CO2 is also produced).

Here is an idea for a novel approach that is Carbon Neutral and solves the H2 infrastructure issue.

Renewable Methanol would be produced from carbon dioxide and hydrogen from renewable sources of electricity (hydro, geothermal, wind and solar) - see Carbon Recycling International (Iceland).

Transported to the H2 station using existing Methanol distribution (pipeline or truck).

At the H2 station, a new approach developed by Georgia Tech, the CO2/H2 Active Membrane Piston (CHAMP) reactor would produce the H2 and capture the CO2 to be recycled back to the Methanol plant. Reference: http://www.news.gatech.edu/2017/02/16/four-stroke-engine-cycle-produces-hydrogen-methane-and-captures-co2.

H2 avenue for future clean energy is evolving fast. This is just one more way of doing it.

Eventually, REs + H2 + FCs will supply fixed and mobile clean energy 24/7 to replace Coal and Fossil Fuels with as much efficiency if not more..

This reforming happens at lower temperature thus taking less energy. Methanol is liquid which can go farther on a smaller volume than gaseous hydrogen. Methanol is inexpensive and can be made with renewable methods.

@Dave, I am very much in favour of the 30Kw range extender idea and IMO, it doesn't much matter what the power source is. It could be petrol, diesel, ICE Methanol or a fuel cell, maybe powered by methanol.
This is because it won't be used all that much - suppose you have a 25 KwH main battery, and a 30 Kw range extender, you are done. The thing is to minimise the cost of this, and that includes fuel storage and emissions control as well as power generation.
It won't be used very much, so the per mile efficiency is not that important. Also, all it has to do is generate electricity, mostly at a steady rate, so it can be simpler than an ICE which must run at a variety of speeds and torques.
A methanol reformer / fuel cell might be perfect for this, IF you had a methanol dispensing network.

Hi mahonj.

Since a fuel cell RE is zero emission at point of use, and does not result in a change of driving characteristics or NVH, the optimum balance of the battery and RE is very different.

There is no point in oversizing the battery beyond average daily use, so I would put the battery component at somewhere in the region of 10-15 KWH.

Not only would this reduce weight, but batteries use a heck of a lot of energy to build them, which hits bigger battery BEVs hard in terms of lifecycle costs in energy and emissions.

So there is no point lugging around or building too big a battery.

@Dave:
"There is no point in oversizing the battery beyond average daily use" - absolutely, I'll accept that, size it to average daily use (+10% ?) and let the range extender do the rest.

That is it! - if we can find a decent range extender of any kind, we are more or less done.

Better still, get "smart" 3kw chargers at people's places of work (just to keep it topped up).

A "smart" charger is one which only charges when the grid is not stressed. You could order (say) 3 kwH power by 5.30 pm with optionally up to 10 KwH if the grid was not stressed (i.e. if there was a lot of wind or solar on the grid).

I am glad that is sorted, we can go to the pub now and see how the implementers are getting on later!

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