# Energy-efficiency aside, what are the chemical constraints on CO₂ capture and methanation?

Synthesising $\ce {CH4}$ from air and water (in a non-biological process) has been proposed as one form of energy storage. What are the chemical constraints at play here? That is to say, what sort of catalysts might be used, and what are the performance / lifetime issues with them?

More specifically:

$\ce {CO2}$ capture and recycling (CCR) has been suggested as one form of round-trip electricity storage, with a round trip being:

• electricity
• $\to$ something that can hang around for hours to months
• $\to$ electricity some time later

The proposal goes something like this: capture the $\ce {CO2}$ produced from the combustion of $\ce {CH4}$ in air in a gas-turbine electricity plant, and store it. Then, when there's surplus electricity, use it to synthesise $\ce {CH4}$ from the $\ce {CO2}$ plus water (I'm guessing electrolysis of water and a Fischer-Trop / Sabatier type reaction). And next time there's a deficit of electricity, burn the $\ce {CH4}$ to generate electricity, and capture the $\ce {CO2}$, and go around again. So, for the sake of this question, I'm specifically interested in the non-biological synthesis of methane.

And let's put aside for one moment the issue of energy efficiency, as that's effectively an economics question. (The question being "is the round-trip efficiency less than the ratio of off-peak to peak electricity prices?") Let's just agree that round-trip energy efficiency is one of the factors that influences the economics, and leave it at that for now.

So the question is: what sort of catalysts might be used, and what are the performance / lifetime issues with them?

• I added some tags I feel are appropriate. I use fixation rather than energy-storage because I feel it better encapsulates both the sequestration and energy storage aspects of the question. – Richard Terrett Jun 26 '12 at 12:05
• I removed the markup from the title, as I think we're moving away from doing that due to how it shows up on searches, please see this Meta post for more details. – jonsca Jul 9 '12 at 5:03
• While it is interesting to pursue better chemical ways to achieve this, we could just grow plants or algae which are already pretty good at the photochemical production of useful products from carbon dioxide. – matt_black Apr 19 '19 at 11:33

I'm only directly attacking your direct question, "what sort of catalysts might be used, and what are the performance / lifetime issues with them?" because the rest is ill-defined. I'll mention some electrochemical conversion aspects. I hope to illustrate why your question is problematic.

There are several different products one could imagine reducing carbon dioxide to:

• methane
• methanol
• formaldehyde
• carbon monoxide
• formic acid
• ethylene

Each will require different materials and conditions, but they all require energy for this to occur. Not to mention, these are all difficult reactions. Thermodynamically speaking carbon dioxide is at the bottom of this energy well and to get out of it requires spending energy.

One approach involves directly electrolyzing on a metal. Cu in aqueous solutions can give methane as a major product, but it also evolves hydrogen and many of the others I listed above. There are a couple of problems with this but the major problem is that it often requires large overpotentials at rates of interest for industrial purposes and this means more cost in terms of electrical input. Another major problem surrounding nearly all of these studies is the selectivity of a catalyst: in water at pH 7 evolving dihydrogen is thermodynamically more favorable than reducing carbon dioxide to everything except methane and methanol. Unfortunately these two are the most complex, as far as chemical transformations are concerned, to make. So the other products are much more likely to be produced along the way. This is why people have focused on making simpler things such as carbon monoxide or formic acid.

Where does this energy come from? Right now coal. So we would end up creating more carbon dioxide than we reduced to other species. It reminds me of how diesel-electric transmission works in freight trains: a dirty engine turns an electric generator that generates electricity that is used on motors instead of the motor directly driving the wheels; I think we can call this diesel-electric transmission an indirect drive whereas the latter is a direct drive. It turns out that making the former is far easier in engineering rather than the latter. The same is true here. It's easier to generate electricity somewhere else then reduce CO2 rather than have energy directly fed to reduce carbon dioxide. You can get efficiencies better by going the latter, but engineering/technical complexities increase immensely.

As a means to address this electrical burden via the direct-drive analogy, people have looked at these artificial photosynthesis approaches, i.e. using light to drive these reactions or at least help ease the energy burden. This requires photocatalysts and often with these come semiconductors. Some semiconductors are naturally good at reducing carbon dioxide, such as CdTe, but this better performance for generating methanol is in turn related to an actual corrosion process of the semiconductor. Semiconductors are very complicated and expensive to manufacture well. They tend to corrode easily when they work well with sunlight. They require catalysts and this introduces huge compatibility issues and manufacturing complexities. We'll just leave the indirect approach at the state the field is, complicated and incomplete.

As for the direct approach:

it's complicated by the fact that carbon dioxide is fundamentally limited in solubility at room temperature. Hence why other people prefer non-water systems. These unfortunately add other complexities...

Actually while typing this I came to the conclusion that I could write a much more succinct response to you rather than continuing to babble on: The best candidate will involve a transition metal, there is no doubt about that. It may end up being a molecular species, but there are so many possible structures that it is hard to say if we won't find a simpler heterogenous catalyst that is more capable first. By Murphy's law, it will be the most expensive material imaginable. But right now, considering everything, you can always look at all extensive work that has been done on copper, but realize it isn't very efficient or selective.

• Thanks for this Chris: if you could write a little about why a transition metal would be the best candidate, I'd appreciate it. – 410 gone Jul 9 '12 at 10:43
• When you first look at the periodic table you can immediately notice the alkali metals on the left and the halogens to the right. Noble gases are normally nonreactive and are being ignored here. Halides as a group tend to be very good at accepting electrons and alkali metals tend to be very good at donating electrons. Reactions such as carbon dioxide reduction require, for a single site, many steps that can be donating or accepting. Transition metals, as a group, tend to have the ability to be very adjustable in their ability to donate or accept e-s and as such are highly useful in catalysis. – Chris Jul 9 '12 at 17:40

Your question was about constraints, but see mostly the ways this could happen: Methanogenic archae can metabolize Hydrogen and Carbondioxide to Methane, the input of electricity would be needed for Hydrolysis. The $H_2$ path of methanogenesis is highly relevant in agricultural biogas plants, so you can probably get the right sort of archae from there or from grass eating animals. For anaerobic digestion in Wastewater treatment plant, the path via acetic acid seems to be far more prelevant, so that's maybe a worse place to look for your methane building workforce. One text on the subject: http://www.zdnet.com/blog/green/h2o-co2-ch4-thanks-to-archaeans/3534 The biological way of storing electricity as Methane is investigated by these guys, I think: http://www.bioferm-energy.com/bf/de_de/company.html

However, I found zero info about how exactly the nearest commercial application ( http://www.solar-fuel.net/ have a pilot plant, the technology doens't handle load changes very well - pity, since that's the entire point) exactly works. I have to assume they use some Sabatier process.

• Thanks mart: the information about archaea is interesting as a side-issue, but I'm focussing here on non-biological synthesis. I've updated the question to emphasise that. – 410 gone Jun 29 '12 at 10:27
• Yes. It seems to me, that the producers (at least the ones I found, all in germany) are very tight-lipped about the specifiy process and catalysts they use. – mart Jun 29 '12 at 10:50
• Thanks for the answer, @mart. For future readers of the question, it would be helpful for you to adjust it to @EnergyNumbers current changes, though. – jonsca Jun 29 '12 at 10:54

One of the earliest reports on the photochemical reduction of carbon dioxide was published about 30 years ago by Jean-Marie Lehn and Raymond Ziessel:

Photochemical generation of carbon monoxide and hydrogen by reduction of carbon dioxide and water under visible light irradiation

Proc. Natl. Acad. Sci., 1982, 79, 701-704

They used Ru(bipy)2Cl2 (the ruthenium complex absorbs the visible light) and CoCl2 as the catalytic system.