Nanocopper CO2 catalyst – a possible solution to EPA's draconian coal power plant killer laws?

From MIT, a possible solution to allow coal fired power plants to meet the new draconian CO2 emission requirements imposed by the EPA. Hybrid copper-gold nanoparticles convert carbon dioxide to methane CO2=>CH4

May reduce greenhouse gas emissions

An electron microscopy image of hybrid gold/copper nanoparticles. Image: Zhichuan Xu

CAMBRIDGE, Mass. — Copper — the stuff of pennies and tea kettles — is also one of the few metals that can turn carbon dioxide into hydrocarbon fuels with relatively little energy. When fashioned into an electrode and stimulated with voltage, copper acts as a strong catalyst, setting off an electrochemical reaction with carbon dioxide that reduces the greenhouse gas to methane or methanol.

Various researchers around the world have studied copper’s potential as an energy-efficient means of recycling carbon dioxide emissions in powerplants: Instead of being released into the atmosphere, carbon dioxide would be circulated through a copper catalyst and turned into methane — which could then power the rest of the plant. Such a self-energizing system could vastly reduce greenhouse gas emissions from coal-fired and natural-gas-powered plants.

But copper is temperamental: easily oxidized, as when an old penny turns green. As a result, the metal is unstable, which can significantly slow its reaction with carbon dioxide and produce unwanted byproducts such as carbon monoxide and formic acid.

Now researchers at MIT have come up with a solution that may further reduce the energy needed for copper to convert carbon dioxide, while also making the metal much more stable.

The group has engineered tiny nanoparticles of copper mixed with gold, which is resistant to corrosion and oxidation. The researchers observed that just a touch of gold makes copper much more stable. In experiments, they coated electrodes with the hybrid nanoparticles and found that much less energy was needed for these engineered nanoparticles to react with carbon dioxide, compared to nanoparticles of pure copper.

A paper detailing the results will appear in the journal Chemical Communications; the research was funded by the National Science Foundation. Co-author Kimberly Hamad-Schifferli of MIT says the findings point to a potentially energy-efficient means of reducing carbon dioxide emissions from powerplants.

“You normally have to put a lot of energy into converting carbon dioxide into something useful,” says Hamad-Schifferli, an associate professor of mechanical engineering and biological engineering. “We demonstrated hybrid copper-gold nanoparticles are much more stable, and have the potential to lower the energy you need for the reaction.”

Going small

The team chose to engineer particles at the nanoscale in order to “get more bang for their buck,” Hamad-Schifferli says: The smaller the particles, the larger the surface area available for interaction with carbon dioxide molecules. “You could have more sites for the CO2 to come and stick down and get turned into something else,” she says.

Hamad-Schifferli worked with Yang Shao-Horn, the Gail E. Kendall Associate Professor of Mechanical Engineering at MIT, postdoc Zichuan Xu and Erica Lai ’14. The team settled on gold as a suitable metal to combine with copper mainly because of its known properties. (Researchers have previously combined gold and copper at much larger scales, noting that the combination prevented copper from oxidizing.)

To make the nanoparticles, Hamad-Schifferli and her colleagues mixed salts containing gold into a solution of copper salts. They heated the solution, creating nanoparticles that fused copper with gold. Xu then put the nanoparticles through a series of reactions, turning the solution into a powder that was used to coat a small electrode.

To test the nanoparticles’ reactivity, Xu placed the electrode in a beaker of solution and bubbled carbon dioxide into it. He applied a small voltage to the electrode, and measured the resulting current in the solution. The team reasoned that the resulting current would indicate how efficiently the nanoparticles were reacting with the gas: If CO2 molecules were reacting with sites on the electrode — and then releasing to allow other CO2 molecules to react with the same sites — the current would appear as a certain potential was reached, indicating regular “turnover.” If the molecules monopolized sites on the electrode, the reaction would slow down, delaying the appearance of the current at the same potential.

The team ultimately found that the potential applied to reach a steady current was much smaller for hybrid copper-gold nanoparticles than for pure copper and gold — an indication that the amount of energy required to run the reaction was much lower than that required when using nanoparticles made of pure copper.

Going forward, Hamad-Schifferli says she hopes to look more closely at the structure of the gold-copper nanoparticles to find an optimal configuration for converting carbon dioxide. So far, the team has demonstrated the effectiveness of nanoparticles composed of one-third gold and two-thirds copper, as well as two-thirds gold and one-third copper.

Hamad-Schifferli acknowledges that coating industrial-scale electrodes partly with gold can get expensive. However, she says, the energy savings and the reuse potential for such electrodes may balance the initial costs.

“It’s a tradeoff,” Hamad-Schifferli says. “Gold is obviously more expensive than copper. But if it helps you get a product that’s more attractive like methane instead of carbon dioxide, and at a lower energy consumption, then it may be worth it. If you could reuse it over and over again, and the durability is higher because of the gold, that’s a check in the plus column.”

Written by: Jennifer Chu, MIT News Office

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Grant Shirreffs

Doesn’t this sound suspiciously like a perpetual motion machine?
No matter how good your catalyst, if the reaction is CO2 + ? => CH4 +?, and you can then burn the CH4 to give CO2+energy, then you must put more energy into the catalyzed reaction than you get from the subsequent burn. So the whole thing seems pretty pointless.

TomL

” Instead of being released into the atmosphere, carbon dioxide would be circulated through a copper catalyst and turned into methane — which could then power the rest of the plant.”
So you convert CO2 to methane (where does the hydrogen come from?), and then burn the methane producing … CO2.
Am I missing something, or does this whole process really accomplish nothing?

Gail Combs

It is a rotten solution.
From the EPA:

Greenhouse Gas Properties
Methane (CH4) is a principal component of natural gas. It is also formed and released to the atmosphere by biological processes occurring in anaerobic environments. Once in the atmosphere, methane absorbs terrestrial infrared radiation that would otherwise escape to space. This property can contribute to the warming of the atmosphere, which is why methane is a greenhouse gas.
Methane is about 21 times more powerful at warming the atmosphere than carbon dioxide (CO2) by weight (see box below). Methane’s chemical lifetime in the atmosphere is approximately 12 years… http://www.epa.gov/outreach/scientific.html

max

Brilliant, in order to handle EPA restrictions on CO2 emmisions to save the planet from waming due to the GHG effect, they propose converting CO2 to methane, a gas with a much greater green house effect (about 20 times that of CO2). I have no doubt that the EPA will run with this announcement to show that their standards are forcing innovation to save the planet.

Besides, isn’t methane (CH4) a much more effective greenhouse gas than carbon dioxide (CO2)?

I’m appalled by the lack of understanding of basic physics of whoever wrote this article. The energy obtained by burning fossil fuels (like natural gas, or CH4) cannot be recovered by reducing CO2 back to methane. Why? Because it would require a source of hydrogen and hydrogen can come only from a catalysed partial oxidation of methane or from the electrolysis of water.
The absurdity of the idea is to suppose that Hydrogen is free and this article gives a very bad name to a otherwise famous institute, the MIT.
It is really shocking ot see how “green thinking” is corrupting science almost everywhere!

John M

Instead of being released into the atmosphere, carbon dioxide would be circulated through a copper catalyst and turned into methane — which could then power the rest of the plant. Such a self-energizing system could vastly reduce greenhouse gas emissions from coal-fired and natural-gas-powered plants.

They’re going to have trouble patenting this, since last I checked, the USPO still dismisses perpetual motion inventions out of hand.

Sparx

Ahhh… April is indeed the cruellest month.

shrnfr

TomL, you missed nothing. Carnot long since demonstrated that perpetual motion machines of the first kind do not exist. That is the first law of thermo. But there is actually a small role these could play. They could be used to take electricity from solar gunk and wind farms and convert it into a storable form.

Kasuha

I guess someone in MIT has drank too much. Converting CO2 into methane requires a lot of energy – at least as much as get by burning it. There’s no way around it as long as first law of thermodynamics applies. And even if they decided to turn all CO2 from power plants into methane – what now with it? Burn it back to CO2? Wouldn’t that be stupid now that we invested so much energy into it? Or release it to atmosphere as methane? Wouldn’t that be even worse than releasing CO2? Or perhaps turn it back into coal?

Jimbo

“……setting off an electrochemical reaction with carbon dioxide that reduces the greenhouse gas to methane….”

Great! Problem solved – methane is now a non-greenhouse gas. Now what the heck do you do with the methane? Burn it? Release it? What?

vboring

Unless it utilizes a waste energy source in the plant, it doesn’t sound like it sould accomplish anything.
Pretend it is 100% energy efficient in converting CO2 + H20 + electricity into methane. Pretend you then burn the methane at 100% efficiency…. and get back exactly enough energy to produce enough methane to fuel the plant that burns the methane to provide the energy to produce the methane… and so on. It does precisely nothing for your coal plant emissions.
One practical use for it theoretically could be to turn cheap nuclear (or surplus wind) energy into easily stored CNG for transportation or back-up power, but as a way to reduce coal plant emissions it is likely worthless.

Doug in Seattle

I have to assume there’s water invloved in the reaction to get some H’s for the methane.
We are still left with the question though of whether CO2 is actually harmful.

Ben

WOFTAM.
Copper has so many gainful uses than to contemplate wastefully throwing it on the fire solely for the purpose of helping gullible warming believers sleep at night.
This sort of nonsense if the reason that the greenpr!cks demonstrable stupidity is so irritating, rather than just being plain amusing

Jimbo

Was this supposed to be a Friday Funny?
REPLY: Is it Friday? – A

Jimbo

Was this suposed to be a Friday Funny?

“Gold is obviously more expensive than copper. But if it helps you get a product that’s more attractive like methane instead of carbon dioxide, and at a lower energy consumption, then it may be worth it…..”

WTF! The propaganda has taken a deep root indeed. Co2 used by plants – very deadly. Greenhouse growers please reduce that 1,000 ppm to a safer 350ppm. Thanks.

sophocles

Hamad-Schifferli said:
“You normally have to put a lot of energy into converting carbon dioxide into something useful,”
==================================
… the foraminifera in the oceans do it pretty cheaply, converting it to calcium carbonate. Oh, yes, that’s right: they’re solar powered.
Much of the world’s CO2 is locked up in limestone. When there’s no more CO2, I guess the foraminifera will be out of a job …

R. de Haan

Those of us who understand the true back grounds behind the CAGW scare know it’s not at all about CO2 reduction.
It’s about centralized control over all our resources, money grabbing, reduction of energy access mobility and population control.
Every “solution” only disturbs their party and will be regarded as most unwelcome.

JuergenK

@Dear Grant
Did you read the whole thing?
Catalysts or enzymes (the biologic pendents of catalysts) do reduce the energy necessary for transformation of a certain molecule into another one. Take Aluminium for example. To melt bauxite you need at least 1200°C. But if you add cryolith the temperatur needed to melt bauxite lowers to about 970°C.
That’s magic – or isn’t it?
No, it isn’t.
The whole life depends on catalysts. We won’t exist, if that magic won’t work.
It is not a “perpetuum mobile”. It is just stuff (copper with gold coat) helping other stuff to get upwards. No, it has nothing to do with energy – but just the way stuff recombines with the little help of a friend 🙂
Please look up catalysts in the encyclopedia of your confidence.

Grant Shirreffs

I understand catalysis. To use a mixed metaphor, it lowers the height of the hill between two energy levels.. But the relative energy levels before and after are still the same, and to move from one compound to another which has a higher chemical potential energy, you need to add energy, The second law makes it quite clear that the amount of energy you have to add will be more than you can possibly get by later burning the product.
My reference to perpetual motion was in respect of their ridiculous claim that by afterwards burning the resultant methane they could increase the efficiency of the plant. I thought that was obvious.

Scott Covert

It’s an interesting process, completely useless for the stated application.
I bet my 14 year old son could debunk this one without any prompting.

Hey, if getting methane out increases the plant’s efficiency by a couple of percent for a modest capital expenditure, I’m for it.

Jimbo

OK, after a more careful read what I understand it that it’s basically a sealed system. Co2 to methane and so on. Still damned pointless and possibly uneconomical, release the co2 and feed the plants. These kinds of projects just fuel (no pun intended) more and more unnecessary schemes.

howarth

I went to the MIT news website and this is an actual article. I thought it was an April 1st article. It still might be. Its dated April 11. This is unimaginable coming from MIT. Rube Goldberg would be laughing. I understand the need for the catalyst but not for scrubing CO2 to convert back to a hydrocarbon. Its a mindless waste of energy
.

John M

JuergenK,
Please look up the difference between kinetics and thermodynamics.
Then write down the possible reactions to make methane from CO2 and calculate the overall thermodynamics (including those needed to make any reducing agents).
Catalysts, no matter how good, can’t drive a reaction “uphill”.

Gail Combs

Paulo Zappi says:
April 11, 2012 at 2:21 pm
I’m appalled by the lack of understanding of basic physics of whoever wrote this article….
____________________________
And to think MIT used to be THE best, sigh….
If this is what now comes out of the best and brightest of US Universities we are in serious trouble here folks.

Where does the hydrogen come from ?
Easy, use coal and the water gas reaction to produce CO and H, combine the H with CO2 from
burned coal in the power plant and complete combustion of the CO generated in the water gas reaction to CO2 …. Uhh …. wait a minute
/sarc
It really is hard to believe that this got to the point of preparing an annoucement with no one asking some basic questions about where do the raw materials come from for the process in a real world application.
One thing to prove it is possible in the lab where you have a handy bottle of hydrogen to feed the reaction of CO2 to Methane and water with a catalyst and voltage input but ——- to put it mildly “WTF”
Larry

AndyG55

Ahhh.. but if you use solar energy to power the converter during the day…. you can use the CO2 over and over again.. and never release it into the atmosphere
Maybe..
Perhaps.
or not.

johneb

The question is whether the conversion of CO2 will be effective enough to keep the EPA off the backs of coal powerplants and be cheap enough that the coal powerplants can still compete with natural gas.

Rob Crawford

OK, so say they convert the CO2 to methane efficiently. When they burn the methane, don’t they get CO2 again?

Wow. If this stuff works, the greenhouse gas issue wouldn’t matter. That methane/methanol looks like low cost fuel to me. Who wouldn’t convert CO2 to fuel just for the economics of it.

Michael J. Dunn

@JuergenK re catalysts
A catalyst does not alter the energy requirement of a reaction; it alters the reaction rate, an entirely different thing. Also, the melting of bauxite is not a chemical reaction, it is a change of state. Adding cryolite creates an “alloy” with bauxite that melts at a lower temperature. There are plenty of such alloys in use (e.g., NaK). And, finally, until and unless the researchers compare the mass of methane generated to the joules of electrical energy used to create it, we will not know the process efficiency.
The implication of this discovery, however, is that one can take cheap nuclear energy, water, and carbon dioxide, and create literally limitless quantities of hydrocarbon fuels (methane can be polymerized into gasoline or kerosene). When the fuel is burned, we close the cycle back to CO2 and H2O and can start all over again. The total quantity of anthropogenic CO2 in the atmosphere cannot increase (as though that mattered). It could be an AGW nightmare.

Urederra

JuergenK says:
April 11, 2012 at 2:43 pm
@Dear Grant
Did you read the whole thing?
Catalysts or enzymes (the biologic pendents of catalysts) do reduce the energy necessary for transformation of a certain molecule into another one.

See? that is the problem. That is not what catalysts do. Catalysts and enzymes reduce the free energy of activation for a certain reaction, meaning that the reaction goes at faster speed, but the energy needed for the transformation remains the same.
If you need 30 kcal to convert the reactants into products without catalysts, you still need 30 kcal with catalysts. That cannot change, it would be against the first law of thermodynamics. What changes is the barrier you have to jump to convert reactants into products. Catalysts reduce the barrier and thus, increase the reaction rate.

Scott Covert

I can see how this scheme might work.
Generate one GW of electricity by burning coal.
Capture 25% of the stack CO2 emissions in a CO2 scrubber.
use 400 MW of electricity to generate hydrogen from water and create methane from the H and CO2.
Burn the methane in a “Green Energy Processor” (on site) generating 200 MW of electricity, let the CO2 escape the stack of the “GEP”.
Claim a 25% reduction in CO2 emissions for your “Clean Coal” plant.
Claim 200 MW of “Green Energy” from your “CEP”.
Dump 200 MW of efficiency to the atmosphere as waste heat with a net loss of 20% in the total process.
Sell the “Green Energy” at 300% markup (Subsidized).
Pay the EPA for your CO2 processing permit.
End global warming!

Brian Adams

Besides, EPA is mainly trying to kill Big Coal, so they don’t want an efficient, cheap, scrubber technology even if it really worked. This would muddle their plans. In fact, if technical solutions to all our “pollution” problems magically appeared overnight, that would obviate the very need for an EPA, wouldn’t it?

Kasuha

Doesn’t even seem to be meant as April Fools joke, unless the whole MIT news office has fallen to one:
http://web.mit.edu/newsoffice/2012/hybrid-copper-gold-nanoparticles-convert-co2.html
Well, yes. They invented a catalyst that can convert CO2 into methane using electricity and some unspecified substance providing enough hydrogen for the reaction.That may be useful if you have lots of CO2 and that unspecified substance, an electric outlet, and need some methane for your laboratory burner. Or maybe someone somewhere will figure out some other good use for it. I just don’t see how could it ever reduce emissions any other way than formally (in the sense we store them here, then handle it over to someone else who takes care of releasing them).

Garry Stotel

I agree with a number of comments here – laws of thermodynamics seem to be ignored in this article, which is so skewed it is almost a propaganda piece, or an alchemy recepie – welcome back to the 16th century, folks.
To reduce CO2 one will need a reducing agent – H2. Which comes from another product of combustion – H2O, breaking up of which will require immense amounts of energy.
And why the hell anyone would want to reduce CO2 emissions anyhow??
FAIL

Catalytic converters on automobiles are also a “magic” gizmo. They convert complex, nasty hydrocarbon gasses and carbon monoxide into plant food and water. CO2 , of course, being the plant food.

SandyInDerby

From a non-chemist could it be (sorry don’t know how to do subscripts)
2 H2O + CO2 + Catalyst + pixiedust => CH4 + 2 O2 + Catalyst?
Which then becomes a perpetual motion machine as CH4 + 2O2 => CO2 + 2H2O + HEAT

Rob Crawford

“Which then becomes a perpetual motion machine as CH4 + 2O2 => CO2 + 2H2O + HEAT”
Except that the energy used to get the CH4 + 2O2 is greater than that released by its combustion.
This sounds like a neat physical chemistry experiment that was overheard by a bureaucrat who demanded they write up a press release explaining how it could be used to combat global warming.

shrnfr

What’s next. Something that reduces the entropy of the universe?? Having a PhD from MIT like I do, I am embaressed that somebody released this in this context. Interesting nanoparticle research and all, but as a way to turn CO2 into CH4 as a practical way to deal with CO2, never mind that dealing with it does not effect the climate, you gotta be kidding.

I thought they were going to make cows stop farting because Methane was worse?
Where will the energy come from to to make the conversion?
I think the collective “we” are out of our rabid-assed minds!

Urederra

AndyG55 says:
April 11, 2012 at 2:52 pm
Ahhh.. but if you use solar energy to power the converter during the day…. you can use the CO2 over and over again.. and never release it into the atmosphere

That is what we do when we plant trees and burn wood.
And that is really 100% natural.
Or, if you want, when we burn coal, release CO2, Plants eat CO2 and grow, they die, they get converted into coal and you have the longer cycle. That is ecology 101,

AlexW

This is the wind gas story. To store the fluctuating wind power you need a CO2 source and a hydrogen source (electrolysis). With this catalyst you might reach 50% to 60% effeciency…
Better than fluctuating wind power, but even more expensive

Justin

This would be interesting if simply released as an innovative approach to stabilize the use of copper as a catalyst… even for the purposes of this particular reaction. In itself, this is probably legitimate research, and a respectable accomplishment. Nowadays, pure research is practically dead, and an unfortunate cycle that this truly exposes involves the use of unsubstantiated propaganda to latch on to the application that will drive the funding for continued research that may or may not be justified in itself. There seems to be a dillusion that marketing should drive technology even to the point of making claims never observed, nor particularly well founded.

JJ

” Instead of being released into the atmosphere, carbon dioxide would be circulated through a copper catalyst and turned into methane — which could then power the rest of the plant.”
This has to be a late April Fools joke. No one at MIT could be that damn dumb.

Ally E.

“Evil CO2” might be the main focus now, but “evil methane” is already in the background. The idiots are already looking at cows in a funny way. It will soon give way to “evil meat” and then we will be stuck with “evil vegetarians”. Oh wait, we already are…

samuellhall

Let us say that in your coal plant, you convert amount X of CO2 into methane. It cost you 1 kw/hr of power to do that. Then you burn the methane ( 25% efficient) and it produces amount Y of CO2. That gives you a net cost of 1000 watt/hr – 250 watt/hr =750 watt/hr to reduce your CO2 emmisions X – Y. THe question is is it worth it?

Katherine

“You normally have to put a lot of energy into converting carbon dioxide into something useful,”
They don’t considering photosynthesis “something useful”?
No photosynthesis = No wheat/corn/rice/soy/vegetables/forage for animals = No meat
What do they expect people to eat? Some exotic stuff that depend on chemosynthesis?

Dr Burns

Why not just go directly from coal to town gas and skip the CO2 generation ? It was all the rage when I was a boy. I still remember the gas spheres and filthy gas works.
Coal + water + high pressure = 50% hydrogen + 20% methane.

Rob Crawford

“Let us say that in your coal plant, you convert amount X of CO2 into methane. It cost you 1 kw/hr of power to do that. Then you burn the methane ( 25% efficient) and it produces amount Y of CO2. That gives you a net cost of 1000 watt/hr – 250 watt/hr =750 watt/hr to reduce your CO2 emmisions X – Y. THe question is is it worth it?”
Problem is, X-Y == 0.