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Researchers at MIT Develop New Water-Splitting Catalyst That Works Under Benign Conditions; a “Giant Leap”

Researchers at MIT—Prof. Daniel Nocera and Dr. Matthew Kanan—have developed a new water-splitting catalyst that is easily prepared from earth-abundant materials (cobalt and phosphorous) and operates in benign conditions: pH neutral water at room temperature and 1 atm pressure. A report on their discovery was published online 31 July 2008 in the journal Science.

The cobalt-phosphorous catalyst targets the generation of oxygen gas from water—the more complex of the two water-splitting half-cell reactions required (H2O/O2 and H2O/H2). Another catalyst generates the hydrogen. Although the new catalyst requires further work, it opens a very promising pathway for the development of systems that use artificial photosynthesis to store solar energy on a large scale in the form of O2 and H2 for subsequent use in a fuel cell.

Of the two reactions, the H2O/O2 reaction is considerably more complex. This reaction requires a four-electron oxidation of two water molecules coupled to the removal of four protons to form a relatively weak oxygen-oxygen bond. In addition to controlling this proton-coupled electron transfer (PCET), a catalyst must tolerate prolonged exposure to oxidizing conditions. Even at the thermodynamic limit, water oxidation requires an oxidizing power that causes most chemical functional groups to degrade. Accordingly, the generation of oxygen from water presents a significant challenge toward realizing artificial photosynthesis.

—Nocera and Kanan (2008)

Other water oxidation catalysts exist, including first-row spinel and perovskite metal oxides; and precious metals and precious metal oxides. The first requires concentrated basic solutions (pH>13) and moderate overpotentials (<400 mV); the second operate under acidic conditions (pH<1).

However, few catalysts operate under the conditions of photosynthesis, i.e. in neutral water under ambient conditions. Neutral water is oxidized at Pt electrodes and some precious metal oxides have been reported to operate electrocatalytically in neutral or weakly acidic solutions. The development of an earth-abundant, first-row catalyst that operates at pH 7 at low overpotential remains a fundamental chemical challenge. Here we report an oxygen-evolving catalyst that forms in situ upon anodic polarization of an inert electrode in neutral aqueous phosphate solutions containing Co2+. Oxygen generation occurs under benign conditions: pH = 7, 1 atm and room temperature.

—Nocera and Kanan (2008)

The new catalyst consists of cobalt metal, phosphate and an electrode, placed in water. When electricity—whether from a photovoltaic cell, a wind turbine or any other source—runs through the electrode, the cobalt and phosphate form a thin film on the electrode, and oxygen gas is produced. Combined with another catalyst, such as platinum, that can produce hydrogen gas from water, the system can duplicate the water splitting reaction that occurs during photosynthesis.

James Barber, a leading researcher in the study of photosynthesis who was not involved in this research, called the discovery by Nocera and Kanan a “giant leap” toward generating clean, carbon-free energy on a massive scale.

This is a major discovery with enormous implications for the future prosperity of humankind. The importance of their discovery cannot be overstated since it opens up the door for developing new technologies for energy production thus reducing our dependence for fossil fuels and addressing the global climate change problem

—James Barber, the Ernst Chain Professor of Biochemistry at Imperial College London

Currently available electrolyzers, which split water with electricity and are often used industrially, are not suited for artificial photosynthesis because they are very expensive and require a highly basic (non-benign) environment that has little to do with the conditions under which photosynthesis operates.

If artificial photosynthesis is to enable the storage of solar energy commensurate with global demand, water-splitting chemistry will need to be performed at a daunting scale. Storing the equivalent of the current energy demand would require splitting greater than 1015 mol/yr of water, which is roughly 100 times the scale of nitrogen fixation by the Haber Bosch process. [The Haber Bosch process  allows the mass synthesis of ammonia from nitrogen and hydrogen.]

The conditions under which water splitting is performed will determine how solar energy is deployed. The catalyst reported here has many elements of natural photosynthesis including its formation from earth abundant metal ions in aqueous solution, a plausible pathway for self-repair, a carrier for protons in neutral water and the generation of O2 at low overpotential, neutral pH, 1 atm and room temperature.

—Nocera and Kanan (2008)

More engineering work needs to be done to integrate the new scientific discovery into existing photovoltaic systems, but Nocera said he is confident that such systems will become a reality. Nocera is the  principal investigator for the Solar Revolution Project funded by the Chesonis Family Foundation and co-Director of the Eni-MIT Solar Frontiers Center.

This is just the beginning. The scientific community is really going to run with this.

—Daniel Nocera

Nocera hopes that within 10 years, homeowners will be able to power their homes in daylight through photovoltaic cells, while using excess solar energy to produce hydrogen and oxygen to power their own household fuel cell. Electricity-by-wire from a central source could be a thing of the past.

The project is part of the MIT Energy Initiative, a program designed to help transform the global energy system to meet the needs of the future and to help build a bridge to that future by improving today’s energy systems.

This project was funded by the National Science Foundation and by the Chesonis Family Foundation, which gave MIT $10 million this spring to launch the Solar Revolution Project, with a goal to make the large scale deployment of solar energy within 10 years.

Resources

  • M W Kanan and D G Nocera (2008) In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+. Science, doi: 10.1126/science.1162018

  • Robert F. Service (2008) New Catalyst Marks Major Step in the March Toward Hydrogen Fuel. Science 1 August 2008: Vol. 321. no. 5889, p. 62010.1126/science.321.5889.620

Comments

gr

The volume of hydrogen at atmospheric pressure which can be generated per square metre of surface is only of the order of 0.2-0.4 cu m/day. At higher atmospheric levels H2 combines with O2 limiting losses to space.

Joe

Lot's of skepticism here, but let's all remember, they laughed at Edison too. Looking for intstant applicability is silly. Science works in lots of baby steps, interspersed every so often with "giant leaps", followed by more baby steps.

Those giant leaps are not often recognized as such by the cognoscenti of the times, but usually only in hindsight. Whether this turns out to be a true giant leap, only time will tell, but it could be, and I am encouraged.

Or is it cold fusion redux? Maybe, but I think this time there's something to it. Now its time for more baby steps.

Unlocking the deep secrets of photosynthesis has been something of a holy grail for botanists and physiologists for decades. What will be interesting to see is how mankind ultimately scrambles to profit from a process mother nature perfected a very, very long time ago. The profit motive has a way of speeding up innovation. Funny how that works.

They say "there's nothing new under the sun", but I am smiling today as I think of old professors and collegues of mine working on photosynthesis back in the 70's, knowing that today, somewhere, they are smiling too.

Kit P

@Joe

I am a little bored with every baby step being labeled as a "giant leaps". Since Joe used the word 'collegues' and indicated he has a science background on the topic, would he please explain the significance of the research rather than prattle on by what 'could be'.

There is large industry of unethical scam artists selling miracle zero energy gadgets, it would be nice professionals behaved professionally by not making irresponsible statement like,

“Nocera hopes that within 10 years, homeowners will be able to power their homes ...”

His statement is irresponsible and unethical because his research field is not in energy conversion systems.

sjc

Andy,

I like it! While you would not get to 100% efficiency, you might get closer. As pointed out, work could be performed on the way up and energy generated there and on the way down.

The O2 is available at elevation for the fuel cell and the water weight and gravity do the rest to create more energy and water resources on the way down...brilliant! It would be good to do the energy in to energy out calculations for this.

Jorge

@ sjc,
Reality Czech already made a calculation of the possible energy (without losses) that can be obtained from hydrogen going up 1 Km, and water coming down 1 Km
It represents about 0.17% of the heat energy of the hydrogen.

sjc

Thanks, I missed his post. I came up with less than 1%, so I come to the conclusion that unless you need the O2 and H2 for a cellulose gasification plant, it may not be worth it.

Joe

Kit P--why don't you unbunch your panties and reread my post. I am actually agreeing with you (but without the contentiousness). In your current state of high dudgeon I assume you missed that part.

I said it was yet to be seen if this is indeed a giant leap. That said, I am hopeful that it is.

One of the points of my post, which i attempted to make in a nice way, was that there has been a lot of research done in the past by good scientists, one of whom I worked for, and one of whom I worked with, and neither of them expected anything more than the respect of their peers for their work.

If this turns out to be a giant leap, then these fellows can take a bow. But when they do, they need to acknowledge the scientists that laid the foundation upon which they stand.

mki

orge or any one els.
Can you recalculate what the percentage of combusted hydrogen power will be if you move balloon of hydrogen from 1KM deep ocean to sea level?
I believe it should be significantly higher.

Kit P

@Joe

Thanks for the clarification. Can you provide info. This happens to be an area that I am interested but do not have a formal background.

Sulleny

Since when does a formal background make one innovative or provide vision? The guy thinks maybe in ten years this process or another like it will allow homeowners to generate some or all of the 10kWh an average home consumes. Big deal. What's unethical about speculation based on peer reviewed science?

What is becoming abundantly clear is the very real probability that some form of electric generator PV/FC, low temp electrolysis, micro-turbine, etc. WILL power single/multiple family residences. Goodbye big grid operators. Good bye corrupt-prone central monopolies. Hello independent, low cost energy. Hello an entire new industry. Hello energy security. 'Bout freakin time.

Unfortunately, the biggest losers in this scenario are old school energy gateways. Which is in reality no loss at all.

joe

@kip--

my specific knowledge of the subject will disapoint you, i'm afraid. Just as looking for instant applicability will be disappointing.

i spent a good bit of time many years ago as a grad student and research associate working in the lab with and for a wonderful, gentle scientist who made learning about the processes of photosynthesis his life's work. I left that field behind over two decades ago, and my knowledge of the science that has occurred since then is lacking.

But i retain a fascination with it because (1) I spent some time studying the process, and (2) because i have always just been amazed by its simple beauty which belies its incredible ingenuity--arguably, the most important chemical process in all of nature, since all of life depends on it.

My mentor often marveled that a process that was first described back in the 1800's would vex scientists for so long. He predicted, back in the 70's, that someday someone would figure out how to duplicate the essence of the photo-based reaction in a way that would allow us to harvest the energy of sunlight the way his blue-green algae did.

When we did, he said we would solve the dilemna that now plagues us. He didn't know how it would do it, just that it WOULD do it.

He was a fine man who i admired greatly, and one of those thousands of quiet bench scientists that contribute the baby steps upon which giant leaps invariably depend, in not only this, but all fields.

It is for that reason that I find myself hoping that the solution by the MIT scientists provides the next stepping stone to making his prediction come true. I do hope it is that giant leap we have been waiting for.

If it is a "giant leap", then eventually they will be acknowledged for it and when they are, I hope they raise a toast to the scientists whose shoulders they stood on to achieve their breakthrough.

My comment about baby steps was purely philosophical in nature, and only intended to acknowledge that this work depended to a great degree on all the research that has come before it.

you are certainly welcome to email me at "gus.lonesomedove@gmail.com" if you'd like to discuss the subject further, but there are obviously other contributors here with a far better handle on the math and energy potential than i have.

I thought Sulleny's comments summed up my hopes on this subject pretty well...."Hello, solution. What took you so long?"

I know for one, I am ready. And I know that somewhere, my friend and beloved mentor is smiling.

Incidentally, my comment "they laughed at Edison", was one of his favorite expressions when people would question him about the abstract nature of scientific inquiry, so that comment was just my way of raising my own toast in his memory.

fakebreaker

"Idiots like jimbo want to replace one large nuke or coal plant with a million H2 home generating systems that will kill your family."

Yeah, but why pay for overpriced, tasteless produce when you can grown your own?

Kit P

Thanks Joe for the thoughtful response. Some of what you are describing is called Industrial Ecology. IE looks at how nature works by taking a waste that a feedstock for something else. IE tries to organize industrial systems to mimic nature. One of the problems is nature is not regulated by the EPA.

One example is a facility that was one of the counties worst polluters while I was studying IE. This facility produced one product and three hazardous wastes that were very expensive to have sent off site. By the time I was working there, the facility produced three products and no hazardous waste.

Post 9/11, this facility had a big security issue because of their method of producing H2.

So I am always looking better way to produce H2.

“Good bye corrupt-prone central monopolies”

This is where I disagree with Sulleny. The electricity generating industry has one of the highest ethical standards that I can find. While making electricity may be characterized by stogy management, I would be interested in the utilities that are corrupt.

I am sure Sulleny does not know what being ethical is about. For example, calling the really nice folks who safely provide electricity 24/7 corrupt would be unethical behavior.

“What's unethical about speculation based on peer reviewed science? “

In my profession, it is unethical to work outside my field of expertize as a professional. If the good researcher, want to debate here fine. If the researcher want to research, the safety of in home energy conversion systems and become a professional in the area, fine.

When researchers speculate to promote their research and suggest dangerous alternatives, that is unethical.

Jorge

@ mki
At 1 Km below sea level the absolute pressure is more
than 100 Kg per square cm !!
I presume that it would take MUCH more energy to split water in H2 and O2 under such an extreme pressure.
Because this process would also have to do mechanical work in expanding an space in the ocean water.

Roger Pham

@joe,

We have mastered artificial photosynthesis, just as we have mastered aerial flying just like the birds, though not with flapping wings but fixed wings.

Artificial photosynthesis is far more efficient (at 10-20% efficiency) than nature's (at under 1-2%). PV panels can convert sunlight to electricity at 15-30% efficiency, then this is used to produce H2 by electrolysis. Then the H2 will be combined with CO2 via Sabatier reaction to produce methane. Methane is a feedstock for the synthesis of longer-chain hydrocarbons. Each further step of synthesis further lowers overall efficiency, so it would be most efficient to use H2 as energy currency, or transitionally, use methane that is pipeline-compatible until a complete H2 infrastructure will be in place.

The problem with plant's photosynthesis, or direct H2 artificial photosynthesis, is that the end product must be harvested in the large field, at considerable increase in energy expenditure and cost. With PV panels or wind electricity, electricity can be harvested and transported far easier simply via copper wires. The end products (H2 and hydrocarbons) will be synthesized and stored at the point of consumption, hence far more efficient logistically.

joe

@pharm and kit

i wasn't necessarily proposing a biological solution as opposed to the applications you've mentioned. that is really interesting information.

what i was reminiscing over was that my old professor told me back in the 70's that someday, somebody would study photosynthesis long enough to finally be able to duplicate what mother nature accomplished over a billion years ago. I can now see that there are multiple solutions, all suggested by the process of photosynthesis.

what this article, as well as the science you have shown me, is that there are multiple applications that can be developed.

on a side note, i will say that while the artificial photosynthesis you mention will have an efficiency advantage over ma nature's solution, since she gives us our fixed production assets for free (grass, trees, phytoplankton), i'm going to bet that the better economic proposition is mother nature's. not that i'm complaining about the new stuff, mind you, but its hard to argue with free from a purely economic point of view :-)

Sulleny

KitP:

One word: Enron. A utility provider of electricity.

And in 2000 California suffered the beginnings of an electric utility regulation crisis that caused repeated brownouts across the state. The mismanagement and bailout cost the taxpayers more than $26 billion dollars.

Big energy, electric and oil have been hotbeds of manipulative scams and schemes for a century. Why defend a clumsy, broken old system that carves up the habitat, loses 30-40% of its energy in transport, and locks consumers into a zero-choice situation?

Energy independence means taking personal responsibility for generation and consumption of one's own energy needs. It is the next step in human energy evolution. Point is Kit, let's get off the big energy teat and start to grow our own.

http://archive.salon.com/news/feature/2001/01/30/deregulation_mess/index.html

Kit P.

ENRON was not a utility. California utilities did recommend building more power plants which were delayed by the regulatory process in California.

Now Sulleny if you are saying the electric utilities are corrupt please show me an example of corruption at electric utility instead of switching to oil or something else.

Sulleny please do not make your own energy. You are too stupid. You will kill the other family members living in your house.

Sulleny

Gosh Kit, I am stupid because I didn't LIST the names of the electric utility companies controlled by Enron for lazy bloggers like you:

* Portland General Electric Company (USA)—serving 775,000 customers in Oregon
* Elektro Electricidade e Servicos S.A. (Brazil)—1.5 million customers
* Compania Anonima Luz y Fuerza Electricas de Puerto Cabello (Venezuela)—50,000 customers

Or any of the *38 electric generating plants* they ran worldwide (look it up genius.)

Do even a minuscule amount of research, and you see that public/private utilities have been the locus of corruption for hundreds of years including present operations like DWP in Los Angeles:

http://ronkayela.com/2008/05/the-news-about-la-just.html


"Energy independence means taking personal responsibility for generation and consumption of one's own energy needs." If you can't handle it KitP -


Lead, follow or get out of the way.

stas peterson

Any body who has studied Science at all knows, that the Second Law of Thermodynamics says there is no process that gets you perpetual motion or something for nothing.

There is no process that starts with oxidized hydrogen splits it into unoxidized hydrogen at a cost of some energy, and then re-oxidizes the hydrogen. to extract some energy,can be anything other then a losing proposition overall.

To profit you must add net energy. And the televangelists, dingbats, wing-nuts, social scientists, publicity flacks, and attorneys, pushing their own religious mantra for either true belief, or cynical power brokering, don't know that, and whatever they do, can't reverse that fact.

They abhor all possible Energy, by religious dogma, so any and all energy sources, as soon as one becomes semi-feasible, will reveal warts and deficiencies, and unexpected side effects, that they then recoil from, waver, and then then denounce.

And promptly go off seeking yet another fantasy of perfectly good energy. Biofuels, stink; Wind sucks; So far geothermal is perfect, so is Solar. Except Geothermal, in practice stinks too, literally. But it's so tiny that no one notices its defects, yet.

Solar so far is preached as the perfect of perfection. The Holy of Holies. So little exists, however, that Thermal Pollution, Albedo Reduction, local climate destruction, plant and animal extinction, and massive land footprints are unrecognized, as yet. But they will be, as soon as some Solar is indeed built.

You have to find Prime Energy Sources and intermittent, variable non-scalable, or energy storage mechanisms, are just not it.

stas peterson

Enron did not create the energy crisis in California. Eco-Wackos and Demo-demagogues did. They did not allow enough electricity generation to be built. Enron had nothing to do with that stupidity.

Enron certainly tried to make a buck and tried to exploit the problem of not enough electricity generation. By acting as a middleman Enron sought to bring foreign power in, to fill the local vacuum created by the religious true believing idiots, NIMBYs, BANANAs, and cynical utility commission demo-demagogues.

Sometimes that meant moving power within California; sometimes importing power from outside the State. Having caught on to the answer, they were cut out as a middleman, and facing bankruptcy the Enron leaders did things badly. But Enron's leaders were frequent campers in the Clinton's Motel, which rented the Lincoln Bedroom to out of town guests.

They thought they bought Democrat protection. What you cynically create, you can cynically destroy, and Enron and its leaders were.

Sulleny

Stan:

There are however intriguing problems with thermodynamics, e.g. the difference between the Sun's surface temperature of 6000'C and the coronal temperatures of some 2 million degrees C.

The data from SOHO observations (now ten years old) indicate that a "magnetic carpet" of tiny opposing magnetic loops could explain the heat the coronal plasma more than 100 times the surface. Thus is born a tremulous theory that heat amplification by vigorous, small magnetic resonance may be possible. The implications of this would certainly confound classic quantum mechanics.

While not directly violating the 2nd law, this scenario does appear to show heat multiplied hundreds of times by abundant, magnetic variations.

Until proven by further observation however, the ratio of the Sun's surface temperature to coronal temperature remains a mystery. Such is the intrigue of science.

Sulleny

Correction:

Solar coronal heat is 1,000,000°C or 1.8 million° F. And the latest NASA TRACE observatory shows solar "ultrasound" waves that may contribute to the mystery heating. Estimated at 1kW/M2 - on solar surface this appears to be related to the much smaller sonoluminescence phenomenon (stellar heat in collapsing air bubbles.)

mki

The problem is that people do understand that 2nd law correspond to close system that is very small as compare to universe.
The whole idea of free energy is not to create something from nothing is to create potential in sea of energy that is around us. The universe do not contain place where there is no difference in energy from one place to the other. If there is difference in energy potential you can used it and you can consider it as free energy. Sun create significant difference in energy potential and we can used that to generate useful energy.

Interesting thing is with passive optical concentrator. They do not required external energy to do the job, however they increase the potential of the energy by increasing the density of energy. The loses (absorption bellow 10%) are relatively low as compare to energy that is concentrated.
I believe that system can be build to concentrate ambient heat if we can overcome the randomness of the direction of heat source ray (the ambient heat is defuse).
Such concentrator can be build by model the shape of concentrator to vortex cone.
This is the only shape where random movement of atoms can be converted to linear movement. I believe same apply to light and heat ray.

Kit P.

@Sulleny

I called you stupid because you do not have a problem calling the people corrupt who provide you a valuable service. You still continue be stupid by falling to do more than name calling.

Yes, PGE was owned by ENRON. However, I am not aware of any corruption at PGE. All the folks I have meet were great leaders and honest.

Same with LADWP who did a better job of ripping off their California neighbors by selling cheap very dirty coal generated electricity than ENRON or anyone else. You did provide a link to a journalist making unfounded allegations. That makes Sulleny a stupid gossip.

Hang in there Sulleny. There is nothing more I would like to see than Jimmy Carter’s boy, S. David Freeman, spend the last years of his life rotting in jail. Yes, it is personal and I would happy to treat you to beverage if you put someone who sounds just like you in jail.

Sulleny is also stupid because he confuses making electricity with energy independence. Sulleny is stupid because he calls for leadership without providing any.

Just so you know, during the 70s and 80s, I reduced importation of oil by safely heating with wood not oil. Since then all my houses have been very efficient all electric homes. My family has never used much electricity, this is called conservation.

Sorry to those who are offended by name calling. Expect it whenever Sulleny demigods the reputation of fine hard working without basis.

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