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Duke team develops new core-shell copper nanowire catalyst for efficient water oxidation for solar fuels

201342press
A transparent film of copper nanowires was transformed into an electrocatalyst for water oxidation by electrodeposition of Ni or Co onto the surface of the nanowires. Chen et al. Click to enlarge.

A team led by Benjamin J. Wiley at Duke University has introduced a new electrocatalyst for water oxidation consisting of a conductive network of core-shell nanowires that is just as efficient as conventional metal oxide films on indium tin oxide (ITO) and a great deal more transparent and robust. A paper on their work is published in the journal Angewandte Chemie.

Water oxidation (2H2O → O2 + 4e- + 4H+) is a key step for converting solar energy into chemical fuels. Nickel and cobalt oxides are attractive anode materials for the oxidation of water because they are readily available and demonstrate high catalytic activity. For use in photoelectric synthesis cells, in which chemical conversions are driven by light, the oxides are typically electrodeposited onto ITO substrates. ITO is used because of its high transmittance and low sheet resistance.

However, the high potentials required for the oxidation of water cause the conductivity of ITO surfaces to fall. In addition, indium is expensive and the production of ITO films is costly. Another disadvantage is that the catalytic oxide layers reduce the light transmittance and thus the light captured by the photovoltaic components.

Herein we report a new approach to create transparent catalysts for water oxidation that eliminates the need for ITO. We replaced the ITO electrode with a conducting network of copper nanowires (CuNWs), which have the advantage of being made from an element that is 1000 times more abundant and 100 times less expensive than indium, and can be deposited using fast liquid-phase coating processes.

We then use electrodeposition to create a conformal layer of nickel or cobalt around the NWs to serve as a catalyst. These core–shell NW networks exhibit sustained electrocatalytic water oxidation with activities comparable to thin films of metal oxides, but transmit up to 6.7 times more light.

—Chen et al.

The nanowire film can also be deposited onto a flexible sheet of polyethylene terephthalate (PET) plastic instead of glass. Unlike ITO-based electrocatalysts on PET substrates, which suffer from significant loss of conductivity after repeated bending, the film made of nanowires isn’t really affected.

This fabrication method can most likely be extended to create core–shell nanowire networks with a wide variety of compositions for various applications. Core–shell nanowire networks exhibit electrocatalytic performance for water oxidation equivalent to metal oxide films of similar composition, but are several times more transparent. The greater transmittance, mechanical flexibility, and lower materials cost of nanowire network catalysts relative to thin film catalysts deposited on ITO opens up new possibilities to engineer more efficient, mechanically robust, and affordable light-harvesting architectures for scalable production of solar fuels.

—Chen et al.

This work was supported in part by the NSF Research Triangle MRSEC (DMR-1121107) and an NSF CAREER award (DMR-1253534). One of the team was supported by a NSF graduate research fellowship.

Resources

  • Zuofeng Chen, Aaron R. Rathmell, Shengrong Ye, Adria R. Wilson, and Benjamin J. Wiley (2013) “Optically transparent water oxidation catalyst made from copper nanowires,” Angewandte Chemie International Edition doi: 10.1002/anie.201306585

Comments

Davemart

Fuel cells after having the most patents granted of any line of technology for years, a common yardstick of both effort and how fast a particular field is advancing, have just dropped into second place, overtaken by solar.

I am wondering how many of the new patents for solar this year are to produce the fuels for fuel cells! :-)

Hydrogen, of course fungible to other fuels such as ammonia, DME and so on, is the missing link for solar, so that it can be stored, shipped and traded.

Jus7tme

A catalyst never can eliminate the losses of a chemical or electrochemical reaction, although it can reduce them somewhat.

The fact remains that taking perfectly good electricity and wasting it on manufacturing hydrogen gas (H2) from water (H2O) is and always will be a net energy and monetary loss compared to using the electrical energy directly,

This fact is just basic physics.

Gorr

Where can i buy these solar fuels, im interrested to buy but they are not selling yet....goddamm *&%¨_

Davemart

Jus7tme:
Perhaps you would detail your cunning plan to have solar available when it is actually needed which does not involve some losses?
The monetary value of power when it is not needed can approach zero, and rise at peak to very high levels.
It is the difference between a useless resource and a useful one.

That fact is just basic common sense.

You had also better inform the plant kingdom that they have got it all wrong turning sunlight into chemical energy.

Jus7tme

Davemart: Your own cunning plan apparently is to apply strawman arguments.But we all know that will not work.

Strawman argument1: Solar is not available when needed

The truth: On the contrary, solar fits well with the profile of peak daytime usage.

Strawman argument2: Hydrogen manufacturing must be good "because, look, plants! photosynthesis!".

The truth: Plants do what they do because that is how they have evolved. So what? It does not logically follow that manufacturing H2 from electricity is good.

Everyone who is scientifically capable and intellectually honest knows that manufacturing H2 is a waste of good energy. Others either believe in the hydrogen fairy or have a self-serving economic agenda.

Davemart

Jus7tme said:

'The truth: On the contrary, solar fits well with the profile of peak daytime usage.'

Wow! is that for the whole world, or just Southern California?
This generalisation is absurd.
I am writing this in the UK, and I can assure you that the sunshine we got in June is not in the least useful now in late October.

Your second 'argument' is just an ad hominem, not a logical proposition.

HarveyD

Intermittent clean energy sources such as Solar and Wind will have to be over-produced and excess energy stored for 'rainy days'.

There are many ways to store excess e-energy and the hydrogen pathway is one of them. Large expensive battery banks is another competing way. Pumping water back into large hydro site reservoirs or other elevated places is another way etc etc.

The best method in one given area may not be so in another place or in another time frame.

Energyfaq.blogspot.com

I think we have a confusion here about hydrogen for transportation, and H2 for centralized storage.

H2 for transportation, especially personal transportation, isn't very useful.

H2 using surplus renewable energy, stored in stationary locations (probably underground, like methane), perhaps converted to other portable forms (ammonia, DME) makes a lot of sense.

Nick

Kit P

“This fact is just basic physics. ”

There is lots of evidence that GCC poster avoided taking science classes when ever possible. There is a area of study called industrial ecology where nature is studied so that industrial systems can mimic nature. Plants take sunlight and make protein to for animals to eat or wood for building material like trees to lumber.

Many things in science is very interesting but not the least big practicl from an engineering point of view. It is very practical to take sunlight and grow plants. Wood can be stored and easily used to produce energy when it is needed.

While interesting, producing hydrogen from the sun rather than attaching the hydrogen to a carbon atom is rather silly.

Davemart

There are umpteen ways of attaching a carbon atom to hydrogen to make transport and storage easier.
Once you produce the hydrogen, it is fungible.
The hydrogen in almost all pathways I can think of offhand is produced first though.

I'm not sure where the notion that hydrogen isn't very useful for transport comes from.
Currently it can power a car, say, for around twice the distance on a tank as the mighty Tesla S gets on its battery pack.
Now battery advocates tend to assume that batteries will improve fast, and drop in price even faster, whilst fuel cells and hydrogen storage, or the use of on-board reformers etc stands still.
In fact fuel cells have been progressing at a faster rate than batteries for years.

It is the old problem of getting a fat person into a corset for batteries.
If you increase the energy density, then something tends to give, longevity or whatever.

The energy density of the total system including the tank of fuel cells systems runs at way over 1kwh/kg, many times the energy density of the very best battery systems.

So writing hydrogen off for transport seems premature, although other things such as DME may be better.

Alain

It is obvious that we will have ever more "excess" electricity, since wind, solar, nuclear, wave and tidal energy (which combined will make most of our electricity in the near future) all will produce electricity largely independent of our needs. As this electricity is ever becoming cheaper, there will be many moments when supply is higher than demand. So why not make H2 from the "free" electricity ?
This will be determined by the capital cost of the H2-generators that will not be productive 100% of the time.
So, if cheap catalysts can be produced, I am pretty sure renewable H2 will be very interesting. Since the electricity almost free, the efficiency of the process does not need approach 100%.
Once cheap H2 is available, it can not only be used to drive cars, but also to produce synthetic fuels from biomass or CO2 with 100% carbon efficiency, or to produce food through organisms (like solazyme or coskata do) or to produce any kind of polymers we use today. Even cellulose can probably be produced cheaper from H2 and CO2 than from trees when large-scale production is built.
Almost everything in your house (except from the stones) consists of more hydrogen atoms than all other elements together. H2 is much more than an energy carrier.

Kit P

@Davemart

You are one of those people who 'avoided taking science classes'. Am I correct? You just say stuff without understanding chemistry of physics.

In nature, one kind of bacteria produces hydrogen but then another immediately produces methane. Why would you want to use hydrogen as a fuel when methane is a better fuel? Chemistry 101! Just for the record, I did not take Chemistry 101 but the much harder chemistry for chemistry majors.

“fungible ”

Hydrogen is not fungible.

“Currently it can power a car ”

Why would you do that or BEV? The ICE using hydrocarbons is very practical. That is how I do it.

I am an engieer, if I have a practical way to accomplish a task I do not go looking for a harder way. I do not have a problem with R&D finding a better way, but so far hydrogen is not it.

I work a lot with hydrogen because of physical and chemical properties but only because there is no other practical choice. Hydrogen is a common industrial gas but not as an energy source.

“So writing hydrogen off for transport seems premature ”

I suppose it does for those who skipped science.

Davemart

'In nature, one kind of bacteria produces hydrogen but then another immediately produces methane.'

Which is why I said that you produce hydrogen first, then if you want to you can add carbon etc.

Your qualifications have not improved your judgement, or your powers of comprehension.

Kit P

@Alain

“It is obvious ”

You could not be more wrong. The power industry produced only the amount of power to meet demand.

Wind, solar, wave, and tidal will never produce much power. While the potential energy is huge, the equipment to produce the power is not very practical. It also has the highest environmental impact.

“So why not make H2 from the "free" electricity ? ”

It is not free, you have to pay people like me to make.

“Once cheap H2 is available ”

That will never happen. Cheap is a relative term.

Electricity is a very commodity when produce with hydroelectric, coal, natural gas, and nuclear. The capital cost of the equipment is expensive. There is a history of consumer complaints when a new power project comes on line. A public utility build a new dam 50 years ago raising the cost of power to the customers to 3 cents per kwh. Today no one complain. Because of the cheap power an aluminum mill came to the area creating jobs.

Then all the 'cheap' power was used up. Since natural gas was cheap gas plants were built but then the price of natural gas went. Now the aluminum mill is gone and the excess 'cheap' power is being sold at market rates.

Kit P


“Which is why I said that you produce hydrogen first, ”

No, you did not produce any hydrogen. Bacteria produced hydrogen. This hydrogen is not available because other bacteria take the hydrogen and produce methane. Methane was produced by the bacteria working together. Also CO2, H2S, NH3OH, N2O2, and N2.

“your powers of comprehension. ”

Davemat does not comprehend science. He just says stuff.

Alain

@Kit P

Let's wait and see what will happen.
But with wind & solar exponancially expanding and prices dropping, I doubt it will take long.
Only Next-gen nuclear is a conceivable alternative.
Wind+solar+nuclear together will (in Europe) by 2025 surely produce the majority of GW.
In France & Belgium it's already the case. Germany is comming very quickly.
(Those 3 countries together is about half the USA-population)
With wind & solar only just taking off, carbon issues increasing and next-gen nuclear looking bright, there is no reason to think the continuous growth would slow down. All 3 are not very cheap to construct, but once operational, they are very cheap to keep online. The same counts for a electrolysis H2 plant.

Germany already sells wind energy often below market price to neighbours, while the giant offshore plants being built are not even operational yet, and solar installations still drop in price and installation rate increases continuously.

The environmental cost of wind & solar is peanuts compared to fossil.
In fact because of this concern, a study performed on the Belgian offshore 300MW windfarm demonstrated a spectacular improvement in biodiversity around the windfarm because the fundations prooved excelent breeding ground for fish and other creatures and offered protection against fishing boats. The fishing industry is developing methods to grow mussels in giant cages hanging above the seafloor in between the wind turbines. In these areas, biodiversity improves and fishing industry gains.

Audi already has a "synthetic natural gas" plant operational to turn ultra-cheap redundant wind energy into H2 and then (with added CO2) into CH4. People do pay the small extra to drive their luxury sportscar on wind energy.
Don't tell the Audi company is run by a bunch of idiots who know nothing about economy.

Maybe at some places on the planet, sun wind and nuclear have no future and renewable H2 will never happen. But I'm not so sure that will be everywhere. Especially in regions where there is no abundant cheap natural gas.


Kit P

Keep letting me know how your system works.

“Let's wait and see what will happen. ”

Based on science and 40 years of power industry experience it will not happen.

“But with wind & solar exponancially expanding and prices dropping, ”

Exponential growth is always followed by die off. That is what has happened to wind in 2013 in the US.

“In France & Belgium it's already the case. ”

Let me point out there are two choices for places without lots of fossil fuel. Import fossil fuel or build nukes.

“Wind+solar ”

Look at the number, wind and solar are shinny things to catch the eye of easily distracted moroons.

If I was marketing a new nuke plants, I would put up a PV system and wind turbines on the site on the site. I would then have a web site that showed power production. If you look around, that is what is done.

“The same counts for a electrolysis H2 plant. ”

Again not true because these plants need large amounts of power.

“Germany ”
Every loon that talks about wind and solar always picks a place that is not like the rest of the world.

“The environmental cost of wind & solar is peanuts compared to fossil. ”

Of course that is not true either. Just for the record, if you are preparing an EIS for a major power project, you have to look at all the environmental impacts. The least of environmental impacts is ghg.

“Audi already has a "synthetic natural gas" plant operational ”

Again not true. There is a giant leap from press releases to doing something. If a new nuke plant design claims a 60 year life life and 95% capacity factor, it is not a big leap for current plants that are running longer than the 40 year design life at 90% CF which is 10% higher than design.

“Don't tell the Audi company is run by a bunch of idiots who know nothing about economy. ”

I will tell you it is just marketing and you would be gullible to believe otherwise. "synthetic natural gas" is a really bad idea from an engineering perspective.

You do not say where you live Alain but you may want to take a road trip. Go to Washington state and look across the river at Boardman, Oregon. Which do yo like better, wind or coal? Then g down to the Mojave Desert and observe the solar plants on your way to Las Vegas to observe the strip. Tell me solar is not just some fantasy when put in context of how we use electricity.

Again, my point is you have to get past press release and judge how things actually work.

Arnold

Kit,
Should we assume a 40yo Masters in chemistry? on it's own is worth a cracker?
That service in the terminally heavily polluting fossil fuel industry is a recomendation.
I understand that fossil fuels are increasingly under the spotlight and the efforts and innovation push to renewables will gain momentum as a matter of necessaty.

To blanket criticise (abuse would be more correct) people who are asking, offering opinion or bouncing ideas reflects a lack of credible argument. E.G. "have you seen the views in Washington etc?" "what would you prefer" I assume you would prefer say CO, as it is odorless and transparent?

Now Jules Verne had no 'masters neither did Leonardo.
That diminishes thier insights?
Sarkosky, any that bring genuine innovation.

But you keep on blasting out how mr clever knows better.
Trying to appear credible by diminishing others is the mark of desperation in the face of no argument to be made.

When blustering is used to silence inquiry, ignorance reighns.I know that people treated that way are too scare to voice an opinion.
If this is how you choose to respond, especially as you claim the sole person to posses intellect, then you can easily be disregared as the same 'loon, of different stripe.

We all need to remember there is a difference between investing (as you would say with money stolen from you) in unproven or still nascent technologies and allowing our imaginative minds to contemplate comment and discuss or communicate these concepts.

When there is useful (even if not currently usable) discoveries to report, surely the correct response is to quietly point out any concerns one may have.

You just might find that people generally respond positively to reason.

Alain

It's funny,

coincidentally there was a press release today where I live in Belgium, and since it was rather windy and sunny, there was an excess of 700MW of nuclear+wind+solar. Now in autumn 2013. We have almost no coal powerplants, and these few are mostly shut down (and will soon be permanently shut down) because of excess power. flexible NG-plants can be activated at peak-hours, but they were also shut down today. (I admit, it's sunday)
Industrial consumers were asked to consume as much as they could today, because in Germany, France and the Netherlands they had the same "problem" of excess power, and therefore there was no demand over there either.

If you have an intrinsic hatred towards solar panels or wind turbines, there is little I can do about it, but I only have to look around me and see ever more cheap solar panels. The solar electricity from my rooftop is really much cheaper then conventional electricity for me, it's very simple math. Ever more people are putting solar cells onto their rooftops, because pay-back time has dropped to only 6 years (without subsidies or tax credits), and after that you have free electricity for the next decade+
Next year, it will be even cheaper.
Far shore wind farms with 7.5MW mills are being erected and will become online next years. It's no science fiction, quite simple math.
And no, we don't build nukes, because they were built 40 years ago. We just keep on using them until there is enough renewable. Next-gen nukes are beïng developed in case they are needed. (if we don't develop them ourselves we can always buy Chinese) The high-voltage DC network is being built across Europe to even-out renewables from Spain to Scandinavia. Part of it is already finished in Germany.

You seem to be pretty sure, that almost the whole world is inhabited by a bunch of morons, stupids and deceived idiots. I say again, we'll see, but it becomes ever more obvious. It's really no difficult math.

Davemart

@Arnold:

the best solution is simply not to read the tripe Kit P pedals which ignores any evidence which does not fit his prejudices, which are that exhaust fumes and coal emissions are good for you.

It may appear as though I read him and respond, but that is not directed to him.

Sometimes I happen to notice a piece of misinformation he is pushing, and in case someone who is unfamiliar with the forum thinks that it might have some sense behind it, I correct it.

That in no way indicates any opening of a dialogue with Kit P, whose views I am entirely disinterested in, but is rather directed to other readers of the thread.

I must admit that I find it quite amusing that this often results in some mult-paragraph response from Kit, as I very, very rarely even bother reading what he has to say in response.

At least he is harmlessly occupied whilst he is typing more of his drivel for an audience which is not going to bother reading it.

Kit P

I just checked my grid, PJM. Today our peak demand is 65,000 MWe below a hot summer day or could winter night.

I want to congratulate Belgium on being able meet its power demand on a mild day. Of course we in the power industry have to meet our customer demands every day.

“Electricity production in Belgium was about 78.6 billion kWh (TWh) in 2012. Of this, in TWh, 40.3 was from nuclear, 20.6 natural gas, 5.8 biofuels and wastes, 5.5 coal, 2.8 wind, 1.7 hydro, 1.7 solar, 0.6 other. Imports were net 9.9 Twh.

Electricity consumption in Belgium has grown from 5800 kWh per capita in 1990 to about 7300 kWh in 2011. Nuclear energy typically provides half of the country's domestically-generated electricity”
http://www.world-nuclear.org/info/Country-Profiles/Countries-A-F/Belgium/

From the information provide above is clear that Alain's post is total BS. There is no '+wind+solar' if you consider that it is a quarter of the power they import. In Belgium, nuclear power is being taxed at punitive rate to subsidize wind and NG.

I will repeat for slow learners like Alain, look at the number, wind and solar are shinny things to catch the eye of easily distracted moroons.

Kit P

“Sometimes I happen to notice a piece of misinformation he is pushing, ”

How would Davemart know what is misinformation and correct it. The best I can tell Davemart is illiterate when it comes to science and engineering.

“prejudices ”

Do you mean like hydrogen fool cells?

Jus7tme

@Alain,

All this prattle about "excess nucelar/wind/solar" is a pack of lies. Look at the source that Kit P linked to above, namely

http://www.world-nuclear.org/info/Country-Profiles/Countries-A-F/Belgium/

and see that wind+solar amounts to hardly anything. All the people who are talking a about "excess green energy" are lying.

Belgium has only been able to provide 5.1% == (2.8+1.7)/(78.6+9.9) of their yearly electrical consumption from wind+solar sources.

Now, propagandists working for the fossile interest have dishonestly defined the word "excess" to mean "any available electrical power production above current demand, assuming that existing fossile plants get first priority in fulfilling the demand".

Do you understand the trick that the propagandists are using here? They define the filthy fossile energy as the first choice and the clean energy as "excess". They then try to sell a pack of lies to the public that we have "excess" clean energy, and fooling the general public into thinking we actually have a surplus of it. We DON'T. The problem is that the entrenched interest of coal and natgas fossile electrical plants are trying to hang on to their market share by defining the other sources as "excess".

What really should be done is to shut down all the coal plants, convert all the natgas plant to rapid response that can be ramped up and down on demand. THAT will minimize fossile fuel usage at all times. Fossile generation capacity is the one that should be defined as excess, and dialed down on demand.

By the way, the 700MW-on-a-Sunday-afternoon fake surplus of solar+wind, how much does it amount to? Per capita of Belgium, it is

700e6/11e6 = 63 watts/capita

About a light bulb per person, much smaller than the average consumption per capita, which is

% 7300/365/24
0.833333333333333 = 833 watts / capita

Are you starting to understand the truth?

Kit P

@Jus7
“What really should be done is to shut down all the coal plants, convert all the natgas plant to rapid response that can be ramped up and down on demand. ”

That is very irresponsible statement just like those made by renewable energy should be 100%. Have you ever seen a modern coal in operation?

It is perfectly reasonable for France and California to not use coal use they have none. Demanding that Wyoming or West Virginia stop using coal is irresponsible. We in the US demanded that fossil power plants install pollution controls and the did. Calling fossil 'filthy' is ignorant. Get with the times

Roger Pham

Did anyone notice the fantastic achievement disclosed in this article? It is about the use of low-cost materials to replace expensive catalysts for solar H2 production yet potential for much higher efficiency. Direct solar to H2 can reduce the cost of separate solar PV and electrolyzer as well as electricity conversion equipments, thereby can significantly lower the cost of solar H2. If the cost of solar H2 will be brought down to be competitive with fossil fuel like NG, then the justification for continual use of fossil will be over. Humanity can start to enjoy RE fuels til eternity!

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