From lemons to lemonade: Reaction uses carbon dioxide to make carbon-based semiconductor

May 21, 2012 By Marcia Goodrich
From lemons to lemonade: Reaction uses carbon dioxide to make carbon-based semiconductor
Transmission electron microscopy image of carbon nitride created by the reaction of carbon dioxide and Li3N.

(Phys.org) -- A materials scientist at Michigan Technological University has discovered a chemical reaction that not only eats up the greenhouse gas carbon dioxide, it also creates something useful. And, by the way, it releases energy.

Making carbon-based products from CO2 is nothing new, but carbon dioxide molecules are so stable that those reactions usually take up a lot of energy. If that energy were to come from fossil fuels, over time the would ultimately result in more carbon dioxide entering the atmosphere—defeating the purpose of a process that could otherwise help mitigate climate change.

Professor Yun Hang Hu’s research team developed a heat-releasing reaction between carbon dioxide and Li3N that forms two chemicals: amorphous carbon nitride (C3N4), a semiconductor; and lithium cyanamide (Li2CN2), a precursor to fertilizers.

“The reaction converts CO2 to a solid material,” said Hu. “That would be good even if it weren’t useful, but it is.”

And how much does it release? Plenty. Hu’s team added to less than a gram of Li3N at 330 degrees Celsius, and the surrounding temperature jumped almost immediately to about 1,000 degrees Celsius, or 1,832 degrees Fahrenheit, about the temperature of lava exiting a volcano.

Hu’s work is funded by the National Science Foundation and detailed in the article “Fast and Exothermic Reaction of CO2 and Li3N into C–N-Containing Solid Materials,” authored by Hu and graduate student Yan Huo and published in the Journal of Physical Chemistry.

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User comments : 35

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ShotmanMaslo
3.6 / 5 (7) May 21, 2012
How much energy does it take to prepare the Li3N?
Mattzm
4.2 / 5 (6) May 21, 2012
How much energy does it take to prepare the Li3N?

Relatively minimal for what comes out at the end. Li3N is prepared through simple heating of lithium in nitrogen atmosphere at temperatures ranging from 180 Celsius to 600 Celsius, though it looks like 300 Celsius is typical. For large scale processing, it would be fairly trivial to combine the two processes so that the Li3N reacting with CO2 is also heating the furnace producing more Li3N.

Source: US Patent 4234554
ShotmanMaslo
1 / 5 (1) May 21, 2012
How much energy does it take to prepare the Li3N?

Relatively minimal for what comes out at the end. Li3N is prepared through simple heating of lithium in nitrogen atmosphere at temperatures ranging from 180 Celsius to 600 Celsius, though it looks like 300 Celsius is typical. For large scale processing, it would be fairly trivial to combine the two processes so that the Li3N reacting with CO2 is also heating the furnace producing more Li3N.

Source: US Patent 4234554


Wait.. such closed loop would be possible? so can this actually be used as an energy source? You take N2, Li, CO2, and produce energy, C3N4 and Li2CN2?
IronhorseA
3 / 5 (2) May 21, 2012
How much energy does it take to prepare the Li3N?

Relatively minimal for what comes out at the end. Li3N is prepared through simple heating of lithium in nitrogen atmosphere at temperatures ranging from 180 Celsius to 600 Celsius, though it looks like 300 Celsius is typical. For large scale processing, it would be fairly trivial to combine the two processes so that the Li3N reacting with CO2 is also heating the furnace producing more Li3N.

Source: US Patent 4234554


Wait.. such closed loop would be possible? so can this actually be used as an energy source? You take N2, Li, CO2, and produce energy, C3N4 and Li2CN2?


Essentially, yes. The end products exist in a lower energy state than the CO2, Li, and N2. So that gets released as heat which can be harvested by appropriate means.
anonperson
5 / 5 (2) May 21, 2012
I checked on the source... they want 35USD to read the whole thing. This article feels like a tease... just enough to get you interested but not enough information to actually go to your friendly college/high school chemistry teacher to verify it...
qquax
5 / 5 (1) May 21, 2012
@IronhorseA, thank you for saying what needed to be said. And shame on phys.org and the press release writer for putting up such a misleading piece.
Kevin_Alix
5 / 5 (3) May 21, 2012
I checked on the source... they want 35USD to read the whole thing. This article feels like a tease... just enough to get you interested but not enough information to actually go to your friendly college/high school chemistry teacher to verify it...


That's actually a pretty standard price for most scientific articles in any discipline... sadly.
Mike_Massen
1.9 / 5 (9) May 21, 2012
Ah brilliant, nature giving us something for nothing in a closed loop thermodynamic cycle, does a deity add a few joules for good measure, where is verkle when you need him ;-)
hithisishal
5 / 5 (3) May 21, 2012
And is there still a net energy gain after reducing lithium?
Sonoran
5 / 5 (2) May 21, 2012
Even if the process requires energy, which it almost certainly does, having a reaction pathway that binds carbon in solid form is a big advantage in regard to carbon sequestration. The big question is the availability of Li in sufficient quantities.
vegetorat
1 / 5 (1) May 21, 2012
@Sonoran Well, seeing as Lithium is one of the most abundant elements in our universe, and our planet, I don't think we are going to have a problem finding any.
words_bleu
5 / 5 (1) May 21, 2012
Will it be practical(heating issues of the exothermic reaction) and feasible(cost wise) to make this reaction happen inside the catalytic converter of automobiles. It would be cool to use this exothermic reaction to warm the car interiors, in winter.
vegetorat
1 / 5 (2) May 21, 2012
@words bleu "Heating issues" oh the hilarity, also, what causes earth raising in temp. is the green house gases. Such as CO2 or methane. Heating isn't the issue, it's the green house gases.
Another thing, cars don't get too 300 degrees celcius. (572 degrees Fahrenheit) Which is required for these reactions to accure.
Mike_Massen
2 / 5 (8) May 21, 2012
vegetorat tried to express status with arbitrary knowledge but failed dismally at distribution and economics
@Sonoran Well, seeing as Lithium is one of the most abundant elements in our universe, and our planet, I don't think we are going to have a problem finding any.
Just because something is {relatively} abundant doesn't mean its economic to extract, details here:- http://en.wikiped.../Lithium

Would be nice if you can suggest a compellingly economic means to extract some of the 230 billion tonnes in seawater vegetorat then I might think you are not wasting our time just seeking self-esteem at our {time} expense...?
vegetorat
1 / 5 (1) May 21, 2012
@Mike Massen we already mass-extract lithium for lithium ion batteries, so there are already ways in which to obtain lithium, relatively easily.
Side Note: I also like how you are so condescending.
Mike_Massen
2.6 / 5 (10) May 21, 2012
vegetorat doesnt realise we are running out of economic sources of Li
@Mike Massen we already mass-extract lithium for lithium ion batteries, so there are already ways in which to obtain lithium, relatively easily..
Did you read the link offered ?

If so then there must be more information you are aware of that is not on this link which you have decided not to share but, continue to make arbitrary claims.

Who is the 'we' you refer to, how are you directly involved in this 'we' to make such far reaching claim ?

Tell me of this "mass-extraction" please ?

Please indicate where/how "..there are already ways in which to obtain Li.." to manage continued sustainability of the lithium battery economy at present or the burgeoning potential for the implementation of the reaction proposed in this article ?

I aim to please and gratified you like my approach to get details out of people who so easily make claims without the ready ease of substantiating their {arbitrary} claims :-)
praeclarum
5 / 5 (2) May 21, 2012
I suspect that this is not a feasible process. Lithium can only be produced by electrolysis, and you are taking very inert products: carbon dioxide and nitrogen gas, and creating something. The only reason this works is because you are using lithium nitride, which is very unstable (nitrides will immediately react with, say, water). Lithium metal does not occur naturally, and you can't produce lithium nitride in, say, aqueous solutions.
gallium
5 / 5 (2) May 21, 2012
The main problem witih this reaction is to have Li and pure N2 to form Li3N. Pure N2 can only be achieved by liquefaction of air which is an energy consuming process too. The conversion of Li to Li3N in technical scale requires absolutely oxygen and water-free conditions. Although the reaction of Li3N and CO2 is exothermic it must be checked carefully if the complete process isn't endothermic. Otherwise one would create energy by the reaction which violates the first law of thermodynamics.
islatas
5 / 5 (3) May 21, 2012
Another thing, cars don't get too 300 degrees celcius. (572 degrees Fahrenheit) Which is required for these reactions to accure.


My pyrometer disagrees with you. Coolant temperature is not equal to engine or exhaust temperature. My exhaust routinely hits 1200 F but normally maintains between 500-800 pre turbo. This is on a little 1.9 TDI engine.
vegetorat
2.3 / 5 (4) May 21, 2012
According to the US Geological Survey, Bolivia's Uyuni Desert has 5.4 million tonnes of lithium. (taken from your own source) China, France, and other countries are currently negotiating with bolivia to start extraction/mining. Read your own sources, then make a sound argument. Also, wikipedia isn't the most credible. There are other ways than electroysis, taking the water in which the lithium is dissolved and boiling it, then raising the tempurature to 180 degrees celcius, and take out only the liquid metal, you have mostly lithium. My oven could do that. Not to difficult. Sure, they may not be doing mass-extraction at this point, and I was wrong about that. We have well over 5.4 million tonnes of Li in Bolivia alone (estimated). We may run out in the future, but it is surely enough to hinder the effect of what the oil companys are doing to this planet. I'm glad you aren't being condescending anymore. It makes me so much more willing to divulge information to you.
kaasinees
1 / 5 (2) May 21, 2012
Deserts are full of energy, so i think energy for mining and processing lithium is very minimal.
Butterfly93
3 / 5 (2) May 21, 2012
Hey vegetorat you dumb git, if you evaporate water containing dissolved lithium you're gonna end up with a pile of lithium salts. Know how you get lithium metal out? Here's a hint it starts with 'e' and ends with 'lectrolysis'. And it takes a buttload of energy.

Stop spreading stupidity.
Butterfly93
5 / 5 (1) May 21, 2012
And the rest of you: if you failed high school chemistry and don't understand the energetic difference between an alkali metal and its salts, just STFU already.
Mike_Massen
2 / 5 (8) May 22, 2012
@Vegetorat
Prior to posting the wikipedia source you claimed we had mass-extraction. Why would you make a claim without data then accept you are wrong only when challenged ?

Are you used to mouthing off rubbish without thought, r u in politics ?

Reminding you of high-school chemistry, you are not going to get lithium metal from your oven ! Thats also rubbish !

Wikipedia *is* a credible source when you check the references, did you ?

I wonder Vegetorat if your thinking is vegetative & your nick 'Vege to Rat' is completely appropriate :-)

Had you provided links/data in the first place or were a researcher or professional commentator in the field I wouldn't have been condescending. Your first comment on this subject showed your ignorance of energy economics & your subsequent comments about your home oven shows great ignorance of chemistry.

When you get an education then you can offer sound propositions.

Until then you speak rubbish & come across as a horribly lazy & bad thinker.
Mike_Massen
2 / 5 (8) May 22, 2012
kaasinees offered potential grammatical ambiguity
.. so i think energy for mining and processing lithium is very minimal.
Absolutely right, after you have transported the lithium to a desert for processing or indeed built costly solar power infrastructure in the desert where they may be lithium there wont be any useful energy/money left over - it will be minimal. That is, a total waste of time.

The exchange rate for energy <-> money is posted on placards and signs all over most cities. This mass guide is a good indicator and offers means to manage the money/energy mix to achieve an industrial outcome but, it is subject to fluctuation.

Despite the GFC we do seem to have the equilibrium shifted too far towards capital and not sufficiently to energy.
Husky
not rated yet May 23, 2012
some of the heat of the reaction between LithiumNitride and Co2 could be used to power electrolysis of the lithiumcyanamide afterward, but there will be efficiency losses, and it will leave you with lithium and cyanogen (CN)2 , or lithium2 and nitrous2 and carbon monoxide, not sure, the latter would be nice as it would recapture pure nitrous as well, the carbon monoxide could be used for the refining of nickel for example, but i think that even if you link all these complicated processed and fiddle around with the waste heat, minimising losses, at the end of the day it would be still like providing the heat for 1 ton of co2 to 300C efficiency losses afterwards, maybe in total, energy rerement of heating a ton of Co2 to 400 C to get you carbon nitride, i don't know if that is favourable to other carbon reaction, but sure is no free lunch.
Husky
not rated yet May 23, 2012
another avenue that i would like to see investigated what co2 does in when exposed to radioactivity, if it can be transmutated or split in an actinedeburner or something, of run carbondioxide through athe melt of a molten salt reactor (wich incidentely contains lithium created on the spot)
Trim
not rated yet May 24, 2012
I wonder if this could be helpful in the future, to help cloud colonies floating in Venus's upper atmosphere to generate oxygen and materials for more floating colonies and even in a million years or so terraform it?
Husky
5 / 5 (1) May 26, 2012
in theory yes, provided you a massive powersource that doesn't create more co2 than it stores, if this energy is no issue of cost and pollution than you wouldn't even need the lithium and dissociate the co2 in a plasma incinirator. For Venus a possible solution would be much larger versions of that australian solar tower concept, rising dozens of kilometers into the venusian atmosphere and have the venusian greenhouse drive the upcurrent and provide gigawatts of electricity for the plasma incinirator, another interesting factor is, that because you effectivly expand the venusian atmosphere, it has more working fluid in the upper layers for adiabatic/radiative cooling into space.
Husky
5 / 5 (1) May 26, 2012
While the australian solar tower was envisioned as 1 km concrete tower, the sheer size of the proposed venusian towers, would take an awfull lot of concrete and pose construction challenges, so I was thinking of an inflatable tower to start with (balloons float pretty easy , even pure oxygen, in the dense venus atmosphere), so, you have this bootstrap inflatable tower, the plasmaburner seperates the C from the O2 and from the C you weave corrosion/heat resistant carbon fiber envelope for the next tower and you inflate it with the lighter oxygen
Skepticus
1 / 5 (1) May 26, 2012
While the australian solar tower was envisioned as 1 km concrete tower,... so, you have this bootstrap inflatable tower, the plasmaburner seperates the C from the O2 and from the C you weave corrosion/heat resistant carbon fiber envelope for the next tower and you inflate it with the lighter oxygen

I like your concept, but I hate to have to push a pin through your Venusian balloons. Getting to Venus with all the necessary tons of hardware, is still in the realm of megaengineering. We are having nosebleeds just to infrequently lobbing a couple of tons to LEO, on the scale you are talking about will certainly bankrupt any space-going nation, even groups of nations. In another century or two, perhaps, when we have worked out a better space drive.
Skepticus
1 / 5 (1) May 26, 2012
It would be great if some expert can point out concrete data re:
- Costs of producing Li: monetary, energy expended and CO2 emissions producing it.
- Costs of producing Li3N: monetary, energy expended and CO2 emissions producing it.
- Money, energy expended and CO2 emissions costs of separating C3N4, Li2CN2, recovery, storage for other uses.
- energy expended and CO2 emissions costs to raise Li3N to 330 degrees Celsius for reaction with CO2.
-Balancing all the above costs with the energy recovered from CO2-Li3N exothermic reaction plus the value of C3N4 and Li2CN2 products and their derivatives.
I guess that there would be no free lunch, energy or CO2 emission wise. The question is whether it is worthwhile to pay to have this lunch.
Urgelt
5 / 5 (2) May 28, 2012
Lithium is abundant in the universe and even on Earth, but that doesn't mean it's cheap to extract it here on Earth.

And so while I find this discovery to be interesting, I doubt it will economically scale to industrial uses.
jmull
not rated yet Jun 13, 2012
I checked on the source... they want 35USD to read the whole thing. This article feels like a tease... just enough to get you interested but not enough information to actually go to your friendly college/high school chemistry teacher to verify it...


I managed to get the full text via my uni. Rxn is 4(CO2) 6(Li3N) > C3N4 Li2CN2 8(Li2O) for those of you who are curious.
AtlasT
not rated yet Jun 13, 2012
It's indeed nice, that the carbon dioxide is consumed - but the production of lithium nitride requires lotta energy and as such it will release a way more carbon dioxide, than it could be consumed by the above reaction.

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