rexresearch
Curtis BERLINGUETTE & Simon TRUDEL
ElectroCatalysis
http://www.fwfuel.com
Corporate Headquarters
#205, 1211-14th Street SW
Calgary, Alberta, Canada T3C 1C4

Research Site
3800 Wesbrook Mall
Vancouver, BC
V6S 2L9, Canada
FireWater Fuel Corp. (FFC) is on a path to make the hydrogen economy a reality by implementing a game-changing catalyst technology for producing hydrogen fuel from water and clean electricity. The high-density hydrogen fuel can therefore act as a storage medium for alternative technologies such as solar and wind, or as a carbon neutral source for hydrogen that is used for other commercial applications. The first generation of the FFC technology demonstrated that a cheap nanoscaled form of catalyst material can help drive the production of hydrogen fuels with little energy input. The performance of the second-generation FFC technology already outperforms the current state-of-the-art in industry. Further exploiting this expertise in advanced materials, FireWater Fuel Corp. is also developing electrocatalyst materials in tandem with strategic multinational partners.




https://www.youtube.com/watch?v=jOYYuVAfTO4
2014 11 21 I²CNER Seminar Series : Dr. Curtis P. Berlinguette
Amorphous Mixed-Metal Oxides Tailored for Water Oxidation Catalysis
Dr. Curtis P. Berlinguette,
Associate Professor, Chemistry and Chemical & Biological Engineering, University of British Columbia, Canada

Friday, November 21, 2014 4:00 p.m.
I2CNER Hall, Ito campus, Kyushu University
Abstract
The conversion of water into hydrogen fuel is a promising scheme for the large-scale storage of solar electricity, but the efficiency of the conversion process suffers from substantial overpotentials. The development of efficient oxygen evolution reaction (OER) catalysts is needed to more easily convert water into hydrogen. We recently demonstrated that amorphous phases of metal oxide films can be accessed through a facile photochemical decomposition technique with precise composition control. This presentation will detail the mechanistic details associated with the electrochemistry of these films that display remarkably high anodic efficiencies.

https://www.youtube.com/watch?v=vszv2BBdUS8
iF Day November 2011 - Dr. Curtis Berlinguette


http://www.vancouversun.com/researchers+hack+high+tech+process+using+heat+lamp/10872598/story.html
UBC researchers hack high-tech process using $10 heat lamp
Bethany Lindsay

VANCOUVER -- A team of UBC researchers has discovered a new way to manufacture a high-tech material using equipment anyone can buy at their local hardware store.
The new technique uses a simple heat lamp — available for about $10 at Home Depot — to create a thin coating of an electro-conductive metal on top of substances like glass, plastic or other metals. The discovery could have applications in everything from generating hydrogen fuels to developing bendable consumer electronics.
“It’s actually a very cheap and accessible method for making a pretty important type of material,” said UBC chemistry professor Curtis Berlinguette, who co-wrote a paper introducing the method.
“You can now do this stuff in your basement.”
The scientists had expected the unorthodox method to work with certain substances, but were pleasantly surprised to find that it was effective with every metal they tried.
“The versatility of the method really did come as a surprise, and that’s where we became quite excited,” Berlinguette said.
Older techniques required expensive chemicals and energy-draining UV light, or even “clean rooms” free from dust and other contaminants. The new process just calls for metal salts to be blasted with the heat lamp for a short period of time.
It would be difficult to estimate exactly how much cheaper the new method is, Berlinguette said, but he suggested it would be “at least an order of magnitude” less expensive. Besides cost, another advantage of the technique is that it can create electro-conductive coatings on plastic without melting it, which means it might be used in things like smart textiles and flexible smartphones.
Berlinguette is hopeful that the discovery could lead to more efficient ways of generating hydrogen fuels through electrolysis, and suggested it might be used for something called an electrochromic window — glass that can darken or become more opaque when electric voltage is applied.
The team believes the method could be used for manufacturing on a large scale and they’re planning to patent their discovery. In fact, they’re already speaking with one company about potential commercial applications.
“This is all still really early-stage stuff. It’s a brand new discovery, so we’re really excited about the potential,” Berlinguette said.
He added that there are still many questions to be answered about the new method, including the optimum temperature range for the heat lamp and the unique properties of the coating it produces. And he said older methods may still be better for certain applications.

https://www.technologyreview.com/s/512996/a-cheaper-way-to-make-hydrogen-from-water/
March 28, 2013
A Cheaper Way to Make Hydrogen from Water

Martin LaMonica

University of Calgary researchers create new method for making water-splitting catalysts using abundant metals.

One of the main barriers blocking wide-scale use of fuel cells is the expensive catalysts used to produce hydrogen fuel from water. Researchers at the University of Calgary say they have developed a novel method for making catalysts using inexpensive metals.
** Two electrodes coated with Fe40Ni60O films produce hydrogen and oxygen from water using less electricity than without a catalyst.

Two chemistry professors — Curtis Berlinguette and Simon Trudel—today published a paper in Science showing how their electrocatalysts perform as well as more expensive materials. They have patented their production method and have formed a company called FireWater Fuel which plans to have a product available as early as next year. The goal is to make an electrolyzer—a device that splits water to make hydrogen and oxygen fuels—that is affordable enough for businesses and consumers.
Their invention is making catalysts from a combination of metals compounds that use iron, cobalt, and nickel. The process, which treats metal compounds or oxides with light, doesn’t require high temperatures.
“The discovery in our paper is the ability to make catalyst films with a uniform distribution of multiple metals,” Berlinguette says. “We use a technique that uses light to decompose environmentally benign precursors in air into our catalytic films. The process is scalable and translates to almost every metal in the periodic table.”  
Conventional catalysts are made with rare or expensive metals, such as platinum. The Calgary researchers’ method produces films that are amorphous in their molecular shape, rather than a crystalline structure. That highly disordered structure actually makes them more reactive.
Harvard professor Daniel Nocera, while at MIT, introduced a low-cost catalyst made of an amorphous cobalt oxide for splitting water to make hydrogen fuel. A company called Sun Catalytix was formed in 2009 using venture and government funding to commercialize his work but it has struggled to make a viable product and has since shifted its focus to making flow batteries. (See, Sun Catalytix Seeks Second Act with Flow Battery.)
Berlinguette says he and Trudel have advanced previous work because their process can be used on any metal on the Periodic Table and combines multiple metals. “Amorphous heterogeneous catalysts are well known,” he says. “The problem is that it is difficult to make amorphous materials with many other metals (than cobalt oxide) and it is infinitely more difficult to introduce multiple types of metals into amorphous films.”
A commercially viable electrolyzer is considered a key component to the long-sought hydrogen economy. A good catalyst can lower the amount of electricity that is needed to produce hydrogen and oxygen from water. The hydrogen would then be stored in tanks and fed into fuel cell to produce electricity as needed.
Initially, FireWater Fuel intends to develop an electrolyzer to produce hydrogen for energy storage at wind farms. It intends to create a commercial prototype of a freezer-size electrolyzer that would convert a few liters of water a day to electricity for consumers by 2015.

http://science.sciencemag.org/content/early/2013/03/27/science.1233638
Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis
Rodney D. L. Smith, Mathieu S. Prévot, Randal D. Fagan, Zhipan Zhang, Pavel A. Sedach, Man Kit Jack Siu, Simon Trudel*, Curtis P. Berlinguette*

Abstract
Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). While most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous mixed-metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to hematite, while those of a-Fe100-y-zCoyNizOx are comparable to noble metal oxide catalysts currently used in commercial electrolyzers.

http://advances.sciencemag.org/content/1/2/e1400215
Science Advances  ( 6 Mar 2015 ) Vol. 1, no. 2, e1400215
DOI: 10.1126/sciadv.1400215
Near-infrared–driven decomposition of metal precursors yields amorphous electrocatalytic films

 Danielle A. Salvatore, Kevan E. Dettelbach, Jesse R. Hudkins and Curtis P. Berlinguette

Abstract
Amorphous metal-based films lacking long-range atomic order have found utility in applications ranging from electronics applications to heterogeneous catalysis. Notwithstanding, there is a limited set of fabrication methods available for making amorphous films, particularly in the absence of a conducting substrate. We introduce herein a scalable preparative method for accessing oxidized and reduced phases of amorphous films that involves the efficient decomposition of molecular precursors, including simple metal salts, by exposure to near-infrared (NIR) radiation. The NIR-driven decomposition process provides sufficient localized heating to trigger the liberation of the ligand from solution-deposited precursors on substrates, but insufficient thermal energy to form crystalline phases. This method provides access to state-of-the-art electrocatalyst films, as demonstrated herein for the electrolysis of water, and extends the scope of usable substrates to include nonconducting and temperature-sensitive platforms.
…We report here a previously untested method for generating amorphous metal-based films, in the reduced and oxidized phases, that relies merely on the exposure of transition metal salts [for example, MClx and M(NO3)x] to near-infrared (NIR) radiation under inert and aerobic environments, respectively (Fig. 1). This method is distinctive from the UV-driven photochemical decomposition of metal complexes (8) in that it is ultimately a thermally driven process and therefore does not require photoactive precursors. Notwithstanding, this NIR-driven decomposition (NIRDD) process furnishes amorphous metal oxide films that display properties commensurate with films prepared by more complex methods and precursors, yet is amenable to curing techniques widely used in large-scale manufacturing processes, including roll-to-roll processing (22, 23). We therefore contend that NIRDD represents a significant advance toward a solar fuel economy, which will invariably require electrocatalysts to efficiently mediate small-molecule transformations. Moreover, NIRDD provides access to reduced phases of amorphous films using moderate experimental conditions. We demonstrate the broad use of this fabrication technique herein by examining the formation of amorphous oxide films containing metals of relevance to the OER reaction [for example, iron (7, 8), iridium (18, 24), manganese (6, 25), nickel (7, 8, 26), and copper (27, 28)]. We also provide evidence that NIRDD, which works despite substrate temperatures not reaching 200°C (fig. S1), can also be extended to substrates that are nonconducting and sensitive to temperature and UV radiation by documenting amorphous metal oxide film formation interfaced with Nafion.
  Fig. 1 Scheme of NIRDD.


The NIRDD of a metal precursor (for example, FeCl3) on a substrate [for example, fluorine-doped tin oxide–coated glass (FTO)] leads to the formation of amorphous metal oxide (a-MOx) and reduced metal (a-M) films under air and nitrogen, respectively.

http://phys.org/news/2013-03-inexpensive-efficient-catalysts-viable-reuse.html
March 28, 2013
New inexpensive, efficient catalysts offer viable way to store and reuse renewable energy


Two University of Calgary researchers have developed a ground-breaking way to make new affordable and efficient catalysts for converting electricity into chemical energy.
Their technology opens the door to homeowners and energy companies being able to easily store and reuse solar and wind power. Such energy is clean and renewable, but it's available only when the sun is shining or the wind is blowing.
The research by Curtis Berlinguette and Simon Trudel, both in the chemistry department in the Faculty of Science, has just been published in Science.
"This breakthrough offers a relatively cheaper method of storing and reusing electricity produced by wind turbines and solar panels," says Curtis Berlinguette, associate professor of chemistry and Canada Research Chair in Energy Conversion.
"Our work represents a critical step for realizing a large-scale, clean energy economy," adds Berlinguette, who's also director of the university's Centre for Advanced Solar Materials.
Simon Trudel, assistant professor of chemistry, says their work "opens up a whole new field of how to make catalytic materials. We now have a large new arena for discovery."
The pair have patented their technology and created from their university research a spin-off company, FireWater Fuel Corp., to commercialize their electrocatalysts for use in electrolyzers.
Electrolyzer devices use catalysts to drive a chemical reaction that converts electricity into chemical energy by splitting water into hydrogen and oxygen fuels. These fuels can then be stored and re-converted to electricity for use whenever wanted.
The only byproduct from such a 'green' energy system is water, which can be recycled through the system.
To store and provide renewable power to a typical house would require an electrolyzer about the size of a beer fridge, containing a few litres of water and converting hydrogen to electricity with virtually no emissions, the researchers say.
Key to their discovery is that they deviated from conventional thinking about catalysts, which typically are made from rare, expensive and toxic metals in a crystalline structure.
Instead, Berlinguette and Trudel turned to simpler production methods for catalysts. This involved using abundant metal compounds or oxides (including iron oxide or 'rust'), to create mixed metal oxide catalysts having a disordered, or amorphous, structure.
Laboratory tests – reported in their Science paper – show their new catalysts perform as well or better than expensive catalysts now on the market, yet theirs cost 1,000 times less.
Their research was supported by the university's Institute for Sustainable Energy, Environment and Economy, Alberta Innovates, Mitacs and FireWater Fuel Corp.
FireWater Fuel Corp. expects to have a commercial product in the current large-scale electrolyzer market in 2014, and a prototype electrolyzer – using their new catalysts – ready by 2015 for testing in a home.
Research details:
What have the two University of Calgary researchers discovered?
They have discovered a ground-breaking way to make new affordable and highly efficient catalysts (called electrocatalysts) for converting electricity into chemical energy. A catalyst is a substance that increases the rate of a chemical reaction.
Why are electrocatalysts useful?
Electrocatalysts are used in electrolyzers, devices that split water into hydrogen and oxygen through a chemical reaction driven by electricity. The hydrogen can then be stored and re-converted to electricity for use whenever wanted.
Scientists have been working for several decades on the problem of trying to make efficient and inexpensive electrocatalysts.
Today's commercial electrocatalysts are typically made of crystalline metal oxides (any chemical compound that has a metal) using rare, expensive and/or toxic metals (e.g. ruthenium, iridium). Such catalysts work well but their prohibitive cost makes them impractical for widespread use, such as in homes and by businesses.
What makes the electrocatalysts created by the U of Calgary researchers different than conventionally made, commercial catalytic materials?
Chemists have traditionally been attracted to creating catalysts out of 'pure' crystalline-structured materials. They've tended to ignore unstructured material as the "crud at the bottom of the flask."
"There really have been few significant advances in catalyst design over the last three decades," Berlinguette says.
He and Trudel developed a novel process that uses cheap, abundant and non-toxic metals (e.g. iron, cobalt, nickel) combined in a highly disordered, or amorphous, structure.
Think of crystalline structures as being like tiles laid in an ordered pattern on a floor, while amorphous structures are like tiles thrown on a floor. Such an amorphous material has no symmetry and is full of 'defects.'
These 'defects' in amorphous mixed metal oxide materials actually make them more chemically reactive – and therefore more efficient catalysts – than crystalline materials.
Laboratory tests by the U of Calgary researchers show their catalysts perform as well as or better than catalysts now on the market – but theirs are 1,000 times cheaper.
"We're essentially showing, even with our 'first generation' of catalysts, that we're equal to or better than anything that's sold commercially right now after 30 years of development," Trudel says.
The researchers say they can utilize any metal in the periodic table and are able to combine as many metals as they want into their catalysts.
"Our fabrication method provides access to an entirely new domain of catalytic materials," Berlinguette says.
What is the significance of this discovery?
The U of Calgary researchers are the first group in the world to utilize their scalable photochemical process to make heterogeneous mix-metal amorphous electrocatalysts for clean hydrogen production.
"As far as we know, there is no other method to easily make amorphous materials where we can combine the metals in any ratio we desire. Now the 'fun' is trying to hit the composition that produces the best catalysts," Trudel says.
What application does their discovery have in the 'real' world?
Having cheap and efficient electrocatalysts would enable homeowners and energy companies to store and reuse, whenever needed, intermittently generated electricity such as solar and wind power.
There is currently no inexpensive way of storing such renewable energy. So electricity generated by the sun or the wind is available only when the sun is shining or the wind is blowing.
Electrocatalysts are used in devices called electrolyzers, which convert electricity into chemical energy by splitting water into hydrogen and oxygen fuels. These fuels can then be stored and reconverted to electricity for use whenever wanted. The only byproduct of such a 'green' energy system is water, which can be recycled through the system.
"This is a completely repeatable and carbon-neutral cycle . . . it's not using carbon at all," Trudel says.
Batteries can also be used to store electricity generated by wind and solar power. However, current battery technology is very inefficient compared with hydrogen, which can store much more energy than batteries.
"The principal role of hydrogen in the energy economy is the storage of solar and wind energy," Berlinguette says.
Cheap and efficient catalysts would provide homeowners and businesses with affordable electrolyzers.
"People could actually start storing renewable energy when it's available and keep that in their house all day and take advantage of it at night," Trudel says.
For example, all of Alberta's wind power farms are located in the southern region of the province where wind conditions are optimum. But when the wind blows, they all produce electricity at the same time.
That drives down the price at which wind farm operators can sell their power to the provincial electrical grid.
What if operators had an affordable way to store that wind-generated electricity, using an electrolyser?
They could then store their wind power as hydrogen, and reconvert to electricity when there's greater demand and they can get a higher price for their clean power.
Electrolyzers with cheap, efficient catalysts could be sized to a homeowner's furnace room, or scaled up to a tractor trailer-sized unit that would store renewable power as hydrogen for reuse by a community, in a 'green' district energy system.
"Electrolyzers effectively enable you to purchase electricity at a discounted rate when there is no demand, and sell back to the grid at peak times," Berlinguette says.
What are the next steps for the U of Calgary researchers?
The researchers are testing various formulations of their amorphous mixed metal oxide catalysts, to better understand the materials and design the optimal catalysts. This includes using proven nanotechnology methods to increase the amount of hydrogen produced.
They also are working toward making a "photo-electrocatalyst," which uses sunlight to increase the hydrogen produced by the electrolyzer.
They have patented both their process for creating their electrocatalysts as well as the new catalysts they've created, and they've established a spin-off company, FireWater Fuel Corp., to commercialize their technology.
The company expects to have a commercial product in the current large-scale electrolyzer market in 2014, and a prototype electrolyzer – using their new catalysts – ready by 2015 for testing in a home.


http://loe.org/shows/segments.html?programID=13-P13-00017&segmentID=5

Low Cost Renewable Energy Storage With Hydrogen

The problem of storing energy from renewable sources is a great limitation of alternative energy technology. The solutions are either inefficient or unaffordable. Host Steve Curwood speaks with Curtis Berlinguette from the University of Calgary about his team's research into a more affordable and efficient mechanism to store renewable power...



WO2016101067
ELECTROCATALYTIC FILMS COMPRISING AMORPHOUS METALS OR METAL-OXIDES PREPARED USING NEAR-INFRARED DECOMPOSITION OF PRECURSORS
 
The present invention provides a method for making materials and electrocatalytic materials comprising amorphous metals or metal oxides. This method provides a scalable preparative approach for accessing state-of-the-art electrocatalyst films, as demonstrated herein for the electrolysis of water, and extends the scope of usable substrates to include those that are non not conducting and/or three-dimensional electrodes.
US20140213441
ELECTROCATALYTIC MATERIALS AND METHODS FOR MANUFACTURING SAME

The present invention provides an electrocatalytic material and a method for making an electrocatalytic material. There is also provided an electrocatalytic material comprising amorphous metal or mixed metal oxides. There is also provided methods of forming an electrocatalyst, comprising an amorphous metal oxide film.