UD catalyst can convert CO2 to CO with 92 percent efficiency
A team of researchers at the University of Delaware has developed a highly selective catalyst capable of electrochemically converting carbon dioxide — a greenhouse gas — to carbon monoxide with 92 percent efficiency. The carbon monoxide then can be used to develop useful chemicals.
The researchers recently reported their findings in Nature Communications.
“Converting carbon dioxide to useful chemicals in a selective and efficient way remains a major challenge in renewable and sustainable energy research,” according to Feng Jiao, assistant professor of chemical and biomolecular engineering and the project’s lead researcher.
Co-authors on the paper include Qi Lu, a postdoctoral fellow, and Jonathan Rosen, a graduate student, working with Jiao.
The researchers found that when they used a nano-porous silver electrocatalyst, it was 3,000 times more active than polycrystalline silver, a catalyst commonly used in converting carbon dioxide to useful chemicals.
Silver is considered a promising material for a carbon dioxide reduction catalyst because of it offers high selectivity — approximately 81 percent — and because it costs much less than other precious metal catalysts. Additionally, because it is inorganic, silver remains more stable under harsh catalytic environments.
The exceptionally high activity, Jiao said, is likely due to the UD-developed electrocatalyst’s extremely large and highly curved internal surface, which is approximately 150 times larger and 20 times intrinsically more active than polycrystalline silver.
Jiao explained that the active sites on the curved internal surface required a much smaller than expected voltage to overcome the activation energy barrier needed drive the reaction.
The resulting carbon monoxide, he continued, can be used as an industry feedstock for producing synthetic fuels, while reducing industrial carbon dioxide emissions by as much as 40 percent.
To validate whether their findings were unique, the researchers compared the UD-developed nano-porous silver catalyst with other potential carbon dioxide electrocatalysts including polycrystalline silver and other silver nanostructures such as nanoparticles and nanowires.
Testing under identical conditions confirmed the non-porous silver catalyst’s significant advantages over other silver catalysts in water environments.
Reducing greenhouse carbon dioxide emissions from fossil fuel use is considered critical for human society. Over the last 20 years, electrocatalytic carbon dioxide reduction has attracted attention because of the ability to use electricity from renewable energy sources such as wind, solar and wave.
Ideally, Jiao said, one would like to convert carbon dioxide produced in power plants, refineries and petrochemical plants to fuels or other chemicals through renewable energy use.
A 2007 Intergovernmental Panel on Climate Change report stated that 19 percent of greenhouse gas emissions resulted from industry in 2004, according to the Environmental Protection Agency’s website.
“Selective conversion of carbon dioxide to carbon monoxide is a promising route for clean energy but it is a technically difficult process to accomplish,” said Jiao. “We’re hopeful that the catalyst we’ve developed can pave the way toward future advances in this area.”
The research team’s work is supported through funding from the American Chemical Society Petroleum Research Fund and University of Delaware Research Foundation. Jiao has patented the novel application technique in collaboration with UD’s Office of Economic Innovation and Partnerships.
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The energy balance of generating and re-burning the CO isn’t terribly relevant. The comparison should be to other ways of creating feedstock and chemicals, period. It may be fine for that purpose. Impact on CO2 emissions and levels is beyond negligible, of course.
Daryl M:
Sorry, but you are very mistaken in your post at January 31, 2014 at 6:28 pm which says
No. I don’t know why you think there was a demand for hydrogen in 1828.
My post rightly said
And part of that wicki explanation says
Richard
From Carbomontanus on January 31, 2014 at 11:19 pm:
Bah! You are a vile burner of charcoal and wood, a lowly creature indeed, who undeservedly besmirches the great reputation of modern forge propane burners!
At the ABANA website (Artist-Blacksmith’s Association of North America Inc.), they host Ron Reil’s old site. A true innovator of modern naturally-aspirated venturi propane burners, he had a decorative metalworking business until recent health problems. Much like yourself, he did blacksmith work, including forge welding, and the casting of iron to aluminum. Might still be doing it too as a hobby, however the old site is now archived.
From his Forge page (yes, the site is messy), you can read about his blacksmithing history, equipment, and his forges, coal and propane, that he has built himself. On the Forge and Burner Design pages you’ll find many designs for efficient and powerful propane burners, that you could cheaply make for yourself from common plumbing fittings. I made an “EZ-Burner” variant myself some years back, it was easy.
There are actually a great many US blacksmiths and other metalworkers who make their own forges, and also potters and glassblowers who make their own kilns. Propane can be very cheap to run.
You said:
Except in these modern times, it’s just not worth it to use such primitive natural materials. You have to invest a lot of heat and time to warm up those dense stones and clays, or even “traditional” hard firebricks, and the investment is lost when you’re done working and the forge is left to cool.
Use the modern lightweight soft firebricks, or the insulating blanket refractory materials like Kaowool. Fire off a propane burner or two, get to welding heat in a minute, have the forge cool right away when shut down and with no burning embers or ashes to worry about.
If you think propane is too expensive for your metalwork, you are obviously using the wrong equipment. Check out the many plans, build your own forge.
CO2 is good for plants and therefore the environment. CO is a deadly poison.
Sounds like a good plan to me if you let those enviro-nuts breath it.
I believe Carbon monoxide is key to the Fischer-Tropsch (FT) process.
http://enerdynamics.files.wordpress.com/2012/07/516px-gtl_process.gif
Forget Carbon capture and storage, think…..
Carbon capture and diesel production.
If we were at the point where we were out of fossil fuels, but we had an robust infrastructure of, say, nuclear power, this would be a good method of producing high energy-density hydrocarbon fuels for moving vehicles, or for storing energy for usage in peak demand periods. But it is by definition not an energy source — it will always be a net energy sink. Oxidizing carbon into CO2 is like letting a cart roll down a hill. Reducing it back into CO is equivalent to pushing the cart back up the hill. By the laws of thermodynamics, it always takes more energy to get it back up the hill than was released when it rolled down in the first place. If they are claiming 92% efficiency, then the energy loss in their process is 8%, so if you expend 100 joules making CO out of CO2, you’ll be able to get 92 joules out of burning the subsequent CO products. The other 8 joules went into heat somewhere — most of it probably from current in the electrical wires. Always a losing proposition. Sorry.
You canna change the laws of physics or thermodynamics. It would have a niche for sure but as a solution for carbon dioxide emissions? Forget it!
John F. Hultquist says:
January 31, 2014 at 10:54 pm
Neither of these compounds play well with their neighbors. Build such plants any place you want but no closer than a 2 hour drive away from my back yard. Just one of the many problems:
http://metallurgyfordummies.com/hydrogen-embrittlement/
===================================================
Thank you very much for the link.
This is the dumbest article you have ever posted. And a further argument for getting the government out of funding research at US universities; there is no science left just broad deep endless irremediable stupidity.
I think I figured out my investment problem.
I’d like to invest in a good idea but Washington and the powers-that-be invest taxpayer money and promote really wasteful, useless and dumb ideas that get them lots of money and power.
I know as soon as I do the people will wake up and make them stop this nonsense.
But, if I invest in a good idea they’ll regulate it until its head is underwater and it dies.
e.g.
Wind mills bad idea – good investment.
Nuclear power good idea – bad investment.
General Motors good idea – bad investment
Hedge fund bad idea – good investment
Oh the ironing.
cn
Richard Courtney,
The water gas reaction using coke as the carbon source was pert of the town gas supply in the UK before the advent of natural gas. One piece of trivia is that the process is the source of the expression of “Being asleep at the switch”. An operator would manually switch the reactors from steam blow to air blow approximately every 20 minutes, a somewhat boring job. Being asleep at the switch would result in the coke mass dropping too low in temperature for the reaction to occur and hence mostly steam being injected into the product gas stream.
Mike Singleton:
re your post at February 1, 2014 at 8:24 am.
Thankyou for that interesting “piece of trivia”. I did not know that and will use it when appropriate.
Richard
Tough crowd.
I wasn’t involved in this study, but I did publish a reasonably high-profile paper on the catalytic reduction of CO2 to CO, some nine years ago, and so I can’t help feeling implicated when various commenters point out that CO is much more toxic than CO2, that the reaction requires a thermodynamic input, that these people are idiots, that this won’t cut down on overall CO2 emissions, and that this study demonstrates why the government shouldn’t fund research at universities.
At the risk of sounding defensive:
– I am not a green cultist. I believe the strongest feedback loops in the study of global warming are confirmation bias and the Texas sharpshooter’s fallacy, and my response to people who get dogmatic about CO2 as the principal driver of climate is, get back to me when you understand clouds. I do not dangle even the theoretical possibility of greenhouse gas remediation in “selling” my research.
– I am well aware that CO is toxic. In fact, a standard line in my talk about this portion of my research is, “So we’ve just turned a nontoxic, nonflammable gas into a toxic and flammable one, which looks like a really stupid thing to do.” But only at a glance is it stupid. Chemists, unlike plants, are really bad at making useful plants out of CO2. We are really good at using CO as our one-carbon building block. In other words, you don’t need to release that toxic gas; you can keep it in the vessel and use it to make some value-added product.
– OK, but the energy has to come from somewhere! Right, so I freely admit I have not, on balance, removed a single molecule of CO2 from the atmosphere. Which is beside the point: Say you think renewables will forever be a boondoggle, but someday we’ll generate all the energy we need from thorium fission, or better yet deuterium fusion. The lowest-tech way to integrate such a boon to mankind with the transportation infrastructure we have now is conversion to high-energy-density chemical fuels. (There’s a case to be made for batteries; my opinion is, we’ll need better batteries.) Look at all the efforts to use hydrogen as that currency. Liquid hydrogen boils at 20K and has a density one-fourteenth that of water. If you can turn CO2 to CO, you can, as pointed out above, make diesel out of that; and there will certainly be better CO2 to liquid fuel conversions down the road if the payoff becomes more obvious. But only if you can run such reactions efficiently, with little wasted energy, would it ever scale. Does this reaction scale? No. Is it a step toward being able to make and break bonds without wasting too much energy? Yes.
– When I get cynical about synthetic CO2 chemistry, I ask myself, what would be the ideal catalyst? Well, it would need to be air- and water-stable. It’d be good if it would take in CO2 at 400 ppm, rather than requiring concentration. It’ll need to take its energy input from light, make a product we need an awful lot of, and it’ll need to be something that scales beyond imagining. Yes, I’ve just described green plants (which I think is why a lot of old CO2 chemists turn to biomass conversion chemistry late in their careers), and yes, there’s a case to be made that even biofuels aren’t going to become viable very soon. Still, there’s something to be said for concentration effects, and again, if you have a nuke plant and want to produce vehicle fuel, turning CO2 to liquid fuels is arguably not an idiotic solution.
JPS:
I write to support the principle of what you say in your post at February 1, 2014 at 8:32 am.
And there is a much, much more important reason for the development of
CO2 –> CO
with great efficiency than production of chemical feedstock.
If it could be achieved then it would be immensely valuable now. I draw your attention to my post in this thread which is here.
The potential benefits of this would be so great that it merits as much research effort as thorium and fusion reactors combined.
And those who are concerned about hydrogen embritlement and the corrosive nature of hot, reducing gas need not be concerned. I solved that problem more than two decades ago as part of my work on the ABGC process.
Richard
Richard, thank you for this, and for your earlier, interesting posts. I’d read that comment but not fully registered it, I think. I’m interested to learn more about this Technion work.
I will add this to my too-long post: It’s hard to get people to pay for your research if you just say, We thought this was fascinating and challenging, so we decided to take a crack at it and here’s what we found. So a lot of papers on CO2 chemistry begin with ritual incantations about CO2 and climate change, and the indirect suggestion that this research might help Solve the Problem.
I don’t like it, and my hero in the field (a real pioneer in fundamental CO2 chemistry) cautioned me early on against ever implying that this chemistry might make a difference in atmospheric CO2 levels.
Get ready, folks are starting to realize that carbon dioxide is a resource to be used, and not a pollutant to be pumped far underground in geological storage! It is a wonderfully useful product, folks will soon be fighting for the rights to buy CO2 from smokestacks.
This New Zealand company converts carbon monoxide into various chemicals via biotechnology:
http://www.lanzatech.com/content/lanzatech-process
I think these schemes are exciting! The first airplanes, cars etc. weren’t especially energy-efficient or cost-effective, but once refinements were determined, they spawned vast new industries. Carbon dioxide could do the same.
Likely, neither are the authors of this study. But they chose to frame their work to fit the green cultist memeset and play to warmist ignorance, by saying absolutely asinine things such as:
And that is why they get the “hard crowd” treatment. They deserve it, for saying stupidly anti-scientific things in and about a putatively scientfic paper, in order to fellate Big Warming and thus keep access to journals and $$$ rolling their way.
This phenomenon is far from restricted to the tiny sub-field of CO2 chemistry, of course. It is pandemic across nearly all scientific disciplines, and is the mechanism by which (similarly anti-scientific) claims of “consensus” are manufactured. Any scientist who participates in this BS deserves to have their hide nailed to the wall.
Richardscourtney, JPS, and Others
Richard: understand your background is in Air Blown Gasification. Nothing personal, but I’m not a real fan of Air Blown Gasification. I’m strictly an the oxygen blown, slurry fed, entrained-flow gasification man. Particularly when it comes to chemical production. No hard feelings. Pros and cons to both technologies. Just an entirely different perspective on my part.
As background, I worked on the Tennessee Valley Authority’s (TVA) commercial scale ammonia from coal project in the mid-1980’s, while working as an engineer and later as a conceptual cost estimator with the TVA’s Fertilizer Research and Development Center. The unit used a Texaco gasifier. Also worked on later proposals to build a 1,000 ton/day ammonia, urea, and electrical power co-production facility using the turbines of a partially built nuclear plant and a series of 2000 ton/day Shell gasifiers. Al Gore killed the Shell project when he became VP, which was a real shame because we would have paid for the entire project within three years of construction. (The USSR collapsed creating a short window of highly profitable ammonia/urea pricing… the window has since passed).
Richard and JPS. Can’t say I agree with you regarding the value of CO for energy storage. For energy storage I’m on the side of air and hydro storage. The TVA Raccoon Mountain facility being a prime example of cost efficient hydro storage. As for air, I believe recent advances in air storage may outstrip even hydro options.
I just can’t see CO chemical storage as being terribly useful for energy storage. Long term, I suspect CO could not compete with fluid battery technologies and I would be more inclined to see scarce research money spent on fluid battery technology instead. (Liquid storage being considerably cheaper/safer than CO storage). Again no hard feelings, just a difference of opinion. If you can reference cost literature I would be happy to reconsider.
As general note to the community (I’m sure Richard & JPS know this), I notice many of you are under the impression that coal is primarily carbon (C). Technically this is not true. Chemically, coal best described as chain of C-H molecules… typically described as C24H12.
For oxygen-fired gasification (in a reducing atmosphere) the partial oxidation reaction is expressed as:
C24H12 + 12 O2 => 24 CO + 6 H2
If chemical production anticipated (or for power applications) the syn-gas is typically processed in dual CO shift reactors via the reaction:
24 CO + 24 H20 => 24 CO2 + 24 H2
Regards, Kforestcat
P.S. I notice that I incorrectly described the partial oxidation of methane in my Jan 31, 2014 at 4:21 post above. I described the reaction as:
CH4 + O2 => 2 CO + 4 H2
This is incorrect (I missed a CH4 molecule) the reaction is properly described as:
2 CH4 + O2 => 2 CO + 4 H2
Sorry, in my hast, I failed to balance the equations.
Kforestcat:
I write to disagree with your assertions in your post at February 1, 2014 at 10:52 pm concerning the usefulness of CO as an energy store.
A fuel is a large store of energy which can release the energy in a controlled manner and not at rapid rate. This is why petrol (US ‘gas’) is a good vehicle fuel, but hydrogen is not: petrol may burn but does not explode in a crash.
Perhaps another illustration may be more cogent for you in the light of your stated background. Burning a kilo of dynamite releases LESS energy than burning a kilo of coal, but nobody would choose to use dynamite as a fuel.
However, you say to me
Oh dear, no. No. No! NO!
Please do not store megajoules as compressed air. It would be a bomb waiting to go off!
This is a classic, “It’s a good idea in the lab,” notion like high-alumina cement but with more fatal consequences. I would not live within a hundred miles of such an energy store because I would not want parts of the nearby towns falling on me when they came back down.
Have you never pricked a balloon?
The benefits of electricity grid smoothing are so great that it would be done if it were viable. Hydro is really, really good wherever it can be used, and if there were sufficient sites for hydro to be a solution to electricity output smoothing then it would be done. Pumped storage is economic for peak demand supply, but is expensive and lacks appropriate sites for it.
You also say
In the days of ‘towns gas’ CO was used as an energy store. Scaling to modern storage would not be a problem of any kind.
The physical size of batteries would be a problem, and fluid batteries also pose severe safety risks. If you think nuclear power gets opposition then think how difficult it would be to get approval for a large liquid battery store. However, the small unit size of such batteries would reduce the novelty risk of their introduction and would enable distributed storage over large areas (although such distributed storage would increase operational and maintenance costs). Anyway, I am extremely doubtful that such large battery operation could be technically viable in the foreseeable future.
CO2 –> CO would be a viable energy store if the conversion had sufficient efficiency. All the safety issues were solved in the nineteenth century when CO was used as a fuel in ‘towns gas’. And the CO is capable of cofiring with other fuels when the energy needs to be recovered. If the efficient conversion could be perfected then it promises to be a method for the needed energy store: indeed, it is the the only viable method which has been evinced to date.
Such an energy store would reduce the need for power stations by about a third and would reduce the difficulties of grid operation.
I only mentioned ABGC because hydrogen embritlement was mentioned in the thread and I failed to resist the temptation to boast that I devised and perfected a solution to that problem. However, none of the advanced clean coal technologies for power generation (including ABGC or yours) is likely to be adopted because of the high capital cost imposed by novelty risk.
Thanks for your comments.
Richard
Richard,
I am curious about your solution for preventing H2 embritlement, can you explain more fully or provide a link. I am not a metallurgist but I am familiar with some methods to avoid H2 attack and embritlement in the refining business.
Also I am curious as to how you would store large quantities of CO comparable to the energy in a million barrels of oil.
Thanks for your reply .
@richard & catcracking
Maybe you ought to know from this side.
We have a boat.
Suddenly and unexpectedly the propellar axis with pin and large button began to “rot” and break. The propellar kept, but was lost after 3 such events. And I had to read about it and ask people.
Common Plumber brass for freshwater does “rot” in seawater. The surface keeps shiny, but inside, it is copper- powder. And fusing on it betrays Cu powder embedded in ZnO.
How can it be possible?
Well protons H+ has to enter and diffuse through that solid metal and oxidize Zn.
To prevent it, the old book from 1915 tells of “Naval brass” containing 2% tin. And what keeps for centuries in seawater is “gunmetal”, high quality mallable tin bronse.
That`s it, and I am not too experienced, but copper you see is also a bit tricky. Brittle copper comes when it is warmed to red hot for too long and allowed to cristallize in too large cristals. It happens for instance also in electric material if that has ran too hot for too long.
And then we have the exotic situation of protons travelling rather easily in the electric lead bond of platinum metals, especially Palladium. Thus also the rumors of possible “cold fusion” by Deuterium travelling the same way.
But Protons H+ travelling rather easily in some metals solid state, that is reality.
Catcracking:
Thanks for the interest you express in your post at February 2, 2014 at 9:11 am.
I don’t know if my method for avoiding H2 embritlement and avoiding corrosion by hot reducing gas would work in the refining industry. I was seeking a method to obtain metals capable of being expansion sections in pipework, sensor shields, etc. in ABGC gas (rich in CO) at ~980°C. We were conducting costly exposure tests on exotic and expensive materials (e.g. Hastelloy X) which were difficult to fabricate, machine and weld. I demonstrated that 310 stainless steel (noted for its high temperature creep resistance) could be electroplated with gold to form a corrosion resistant barrier. A copper bond coat is needed between the steel and the gold. I was concerned that mercury from the gas would destroy the protective layer by forming an amalgam. However, theoretical calculations indicated the Hg would evapourate faster than it could diffuse into the Au, and this proved to be the case. The protective layer is only a few microns thick and needs protection from erosion by dust in the gas stream, but this is simply achieved by a protective barrier of ceramic cloth.
This solution was much cheaper than the exotic materials being tested, and 310 ss does not have the fabrication problems of the exotics.
An unexpected finding was that hydrogen does not cross the electroplated barrier into the steel. I do not know why. I have reason to think it is the Cu bond coat (not the Au) which inhibits the H2 passage. I have a few ideas about why this happens but could not pursue them because the Coal Research Establishment where the work was conducted was closed as part of the closure of the UK coal industry.
An interesting point is the reluctance of engineers to testing of the protective Au-layer idea. I suspect the prejudice was because they had a subconscious idea of a gleaming gold-plated chemical engineering plants. However, the Au-coated 310 ss works, is much cheaper than the exotic materials, and the obvious fabrication problems of the exotics are avoided. The used amount of gold is very small and cannot be stolen.
You ask how to store “quantities of CO comparable to the energy in a million barrels of oil”. A barrel is about 1.7 MWh so you are asking for storage equivalent to enable a 2GW power station to operate for about an hour. I see no problem constructing sufficient gasometers for that. Indeed, about 3 times that would be needed for complete output smoothing from a single 2GW power station, and that need not be problematic for a new plant.
I hope that is what you wanted.
Richard
Carbomontanus:
Thanks for your post at February 2, 2014 at 9:54 am which you provided while I was typing my post at February 2, 2014 at 10:14 am. I did not ignore your post: I did not see it until I had posted mine.
Yes, as my post says, I was surprised by the apparent effect of a 3 – 5 micron electroplating bond coat of copper between steel and gold. There is work to be done here because I don’t understand how and why the copper layer inhibits passage of hydrogen at temperatures at ~980°C, but I know it does.
Richard
Carbomontanus,
You are correct, as a long time boat(s) owner in salt water, I am well aware that normal copper does not cut it in salt water. One must user Naval quality usually Bronze for strength. Many a boat has been sunk with using the wrong valves or other fittings for thru hulls and other piping for equipment such as sea water used for wet air conditioning systems. I have a concern when I purchase fittings today that the foreign made fittings might not be suitable although the packaging claims it is suitable for salt water.
Richard,
Thanks for your reply,
I’ll keep that in mind as another means to protect steel, it is interesting although I have already taken heat for silver plating Ring Type flange gaskets. I assume you are talking about low pressures whereas in the Refining and Chemical business we are mostly at higher pressures.
In most high temperature applications we try via refractory linings to keep the metal temperature below 650 F even in expansion joints.
Also I find your storage tanks interesting especially after reading that water seals are used at the telescoping joints, although I don’t have a grasp of the details. The leakage issue initially raised concerns in my mind as to storage issues. As a child I used to pass a telescoping gas tank often and always wondered how they seal from leakage.
I still have significant skepticism about the catalytic process described in this post particularly on a commercial scale since separation of Nitrogen from the CO2 would be expensive where air has been used for combustion.
BTW the Cat in my name (catcracking) is an abbreviation from Fluid bed Catalytic Cracking which is a key high temperature processing stage employed in most oil refineries where we use refractories, expansion joints and high Ni Cr steels.
Again, appreciate your reply
Actually pure copper is relatively resistant to corrosion in seawater. What you are talking about is brass, a copper alloy using zinc and copper – most copper tubing is close to pure copper but the fittings used to join the tubing are mostly brass. The process which you described as rotting is a type of corrosion known as dezincification, and results in a spongy looking mass of copper which has no strength and leaks like a sieve. Tin or antimony added to brass will reduce the corrosion and is classified as corrosion resistant brass. Gunmetal is bronze and is an alloy of copper and tin and is resistant to corrosion. Naval or Admiralty Brass, was developed by the Royal Navy specifically to resist the corrosive effects, and is composed of approximately 69% copper, 30% zinc, and 1% tin. I’ve actually found that nickel brass (70% copper, 24.5 zinc, and 5.5% nickel) is the most effective for use in seawater, but is usually more expensive.
Zinc is frequently used as a sacrificial anode on seawater systems to protect against corrosion of other metals – if you are using a marinized engine look for the anode plugs, if you are not using a marinized engine, get some anodes fitted or your engine will be toast within a year or less. Same goes for any systems in contact with seawater or using seawater as their coolant.
BTW don’t use aluminum in contact with seawater – it corrodes very quickly, and if you use it connected to any stainless fittings it will bond like its welded making it very difficult to remove.