Spanish Researchers Claim a Green Hydrogen Breakthrough

Guest essay by Eric Worrall

Researchers in Spain claim their breakthrough cuts the cost of electrolysis cells, by replacing the traditional arrangement of layered electrode plates with a much simpler electrochemical system.

H2? Oh! New water-splitting technique pushes progress of green hydrogen

It’s really dope. Yep it’s an energy-efficient process kicked off by gadolinium-doped cerium dioxide

Lindsay Clark Tue 3 Nov 2020 

Researchers in Spain have uncovered a new approach to producing hydrogen via water splitting which could help overcome some of the drawbacks to this promising alternative fuel source.

In a study published in Nature Energy, Valencia University researcher José Manuel Serra, professor José M Catalá-Civera, and their colleagues describe a method for producing hydrogen gas by blasting microwave radiation at a watery chemical soup. The approach could make extracting hydrogen from water cheaper, and more importantly, reduce the capital costs of the necessary machinery.

The cyclical process proposed by the research team uses a soup of gadolinium-doped cerium oxide and water. Applying microwaves to the mixture electrochemically deoxygenates the cerium oxide, but when the microwaves stop, there’s a reaction with the water, and the cerium re-oxygenates and produces free hydrogen.

Read more: https://www.theregister.com/2020/11/03/greener_hydrogen_via_water_splitting/

The abstract of the study;

Hydrogen production via microwave-induced water splitting at low temperature

J. M. SerraJ. F. Borrás-MorellB. García-BañosM. BalaguerP. Plaza-GonzálezJ. Santos-BlascoD. Catalán-MartínezL. Navarrete & J. M. Catalá-Civera 

Supplying global energy demand with CO2-free technologies is becoming feasible thanks to the rising affordability of renewable resources. Hydrogen is a promising vector in the decarbonization of energy systems, but more efficient and scalable synthesis is required to enable its widespread deployment. Here we report contactless H2 production via water electrolysis mediated by the microwave-triggered redox activation of solid-state ionic materials at low temperatures (<250 °C). Water was reduced via reaction with non-equilibrium gadolinium-doped CeO2 that was previously in situ electrochemically deoxygenated by the sole application of microwaves. The microwave-driven reduction was identified by an instantaneous electrical conductivity rise and O2 release. This process was cyclable, whereas H2 yield and energy efficiency were material- and power-dependent. Deoxygenation of low-energy molecules (H2O or CO2) led to the formation of energy carriers and enabled CH4 production when integrated with a Sabatier reactor. This method could be extended to other reactions such as intensified hydrocarbons synthesis or oxidation.

Read more: https://www.nature.com/articles/s41560-020-00720-6

Cerium is a rare earth mineral, mostly extracted in China. The current world price for Cerium Oxide is around $1800 / ton, though this could rise if everyone suddenly needs Cerium for their green revolution hydrogen electrodes. Having said that, Cerium is the 26th most abundant element in the Earth’s crust, more abundant than lead, so in principle there is plenty of Cerium available to extract if demand rises.

It will be interesting to see how well this process scales out of the lab. The most common problem with catalytic processes like this is impurities in the water poisoning the catalyst. As water is electrolysed, it would tend to leave behind and concentrate any unwanted contaminants in the Cerium Oxide.

For example if some of the Cerium catalyst came in contact with sulphur instead of oxygen during the hydrogen production phase, because the water being electrolysed was contaminated with a small amount of sulphur, the resulting Cerium sulphide ceramic might be durable enough to survive the microwave regeneration phase.

Despite the potential cost saving of this new catalyst, the green hydrogen produced by this generator is still very expensive, because of the cost of the renewable energy which is required to fuel the process.

80 thoughts on “Spanish Researchers Claim a Green Hydrogen Breakthrough

  1. To me invoking the Sabatier process into the equation rings warning bells as it is really a rather pointless exercise; but perhaps I have read this wrong.
    The fact however still remains :- Producing Hydrogen is always going to be an expensive process without reliance on fossil fuels.

    • “Producing Hydrogen is always going to be an expensive process without reliance on fossil fuels.”

      No doubt. And of course, it takes more energy to uwave the cerium oxide back to cerium then you get from the H that’s released when the cerium is oxidised.

      • As for all this talk of hydrogen, it is NOT a “source” of energy , it is a transport mechanism and not a very safe, easy or reliable one at that.

        As water is electrolysed, it would tend to leave behind and concentrate any unwanted contaminants in the Cerium Oxide.

        Exactly, you basically need to start with distilled water ( as they certainly did in this experiment ). That makes it totally impracticable at scale.

      • And the article stated price of Cerium metal of about a buck a kilogram is out by a couple of orders of magnitude should you try to actually purchase some….

  2. And storing hydrogen is very difficult. It is such a small atom is readily escapes confinement. It is reactive with most metals. And has very poor compressibility.

    • On top of that I understand hydrogen to be a battery, not a fuel. More goes in than comes out, energy wise.

    • There is a lot of work going on to use ammonia (made with renewable hydrogen) to power large ships. link

      For years, people have been talking about the hydrogen economy. Hydrogen storage is a huge hurdle in the way of implementing that. Ammonia fuel solves the storage problem … but raises another problem which is that ammonia is highly toxic.

      • The only Hydrogen economy that makes sense is based on Deuterion/Proton fusion with He3 as the ‘combustion’ product. The ‘exhaust’ is more valuable than the fuel and it comes out as a fast moving positive charge which is relatively easy to convert into useful electricity. If you can take advantage of the EM moments of the Deuterion to align the neutron in a specific orientation, it should be easier to initiate fusion by shooting protons directly at the neutron side where the force of charge that must be overcome is much less than fusing from the proton side. It only produces a couple of MeV per fusion reaction, but the same neutron alignment technique can then be used for D-He3 fusion where the protons produced here becomes the protons creating the He3 from the D and the result is nearly 20 MeV per fusion reaction as fast moving charges readily converted into useful electricity with no radio active byproducts or high speed neutrons, whose final exhaust is benign He4 and whose fuel is as safe to store and transport as water. Of course, you wouldn’t bother with cerium decomposition of heavy water to generate Deuterium, as the electricity required to split D2O is otherwise free.

        The eco-nuts will probably complain that all the Helium released is increasing the pitch of bird calls by .0001 Hz per year and the birds will eventually no longer to be able to recognize each other in order to mate.

    • Somewhat true, but compressed hydrogen use is common and is achieved through the use of appropriate metallurgy to avoid embrittlement, etc. Refineries continually produce and use tremendous amounts of hydrogen for hydrotreating and hydroprocessing.

      The above concept likely overcomes electrochemical issues that shorten the life of electrodes.

    • Microwave equipment can also be run with nuclear energy, which would be much cheaper than using solar cells for that. The best energy storage will remain hydrocarbons, due to the ease of handling, and most of all their energy density. If one can produce them by reduction of CO2, then maybe a carbon neutral hydrocarbon economy is possible, although the costs for these fuels will be much higher than that of fossil fuels, since you have to put in the energy first, possibly with low to medium yields.
      Due to the fact that CO2 is NOT a problem, but is rather beneficial for mankind, I don’t see the point in this anyway.

  3. Er… Does hydrogen go bang very easily, hence why vehicles are not hydrogen powered? Also I have learnt a very simple thing about life, No matter what we do in life, we will need fossil fuels, and green is not green, in fact it is a scam.

    • Hydrogen has a very broad flammability range—a 4 percent to 74 percent concentration in air and 4 percent to 94 percent in oxygen; therefore, keeping air or oxygen from mixing with hydrogen inside confined spaces is very important.
      explosive lessons in hydrogen safety – NASA
      The Hindenburg comes to mind.

      • Gordon

        I also had an up close & personal experience with hydrogen generation & burning in a Ga Tech freshman chemistry lab. As I recall, this resulted in my using the emergency shower for a couple minutes before returning back to the dorm to change clothes.

        Being a college student & male, I did laundry about once a month; the shirt I had worn in the lab simply disintegrated in the laundry bag.

    • Agreed. What is green about burning a fuel that priduces water vapour that is a GHG that is 5-10 times more powerful than CO2?

  4. I’m not a chemist or a materials scientist so I won’t speculate but what are the input vs. output numbers? Does it take more energy input than the output? Just wondering.

    • The laws of thermodynamics always apply.

      You Can’t Win
      You Can’t Break Even
      Once You Start You Can’t Quit The Game
      You Have To Play

      Of course it’s a net energy loss and entropy gain… But they hand-wave it away with “Renewable Energy Source” as if these are a free way to square the circle.. But these are just as bound by physical law …

      • Hoped someone with knowledge would answer “Isn’t this also the case with ethanol?”

        I think, in practical terms it depends of the source of the ethanol.
        Ethanol from a fermenting, for example SugarCane or methane from a chemical process.
        I guess there is more energy put into the whole fermenting process compared to the energy put into the chemical process. But the latter means use of fossil fuel, which you would normally burn directly, if you are not insanely Green.

        • You can get useful energy from a process provided you are able to ignore, or at least not pay for, parts of the overall system..

          e.g

          Alcohol: you had to buy the crops, fuel the fermentation, cleaning racking, pumping etc.. Provided the price of the output covers the costs and yields a profit you don’t care about the Solar energy input, the energy burnt in clearing, plowing, weeding, harvest and transport, the energy content of husks and stalks….

          Nuclear: There’s the cost of construction and maintenance, mining refining and delivering the fuel. You don’t have to account for the energy spent in the inefficient fusion of smaller nuclei into unstable ones that can be persuaded to disintegrate.

  5. H2 production via water electrolysis mediated by the microwave-triggered redox activation of solid-state ionic materials at low temperatures (<250 °C).

    They are doing this with a supercritical fluid? With H2 in the vessels?

    That will certainly scale to industrial production with no problems!

  6. Applying microwaves to the mixture electrochemically deoxygenates the cerium oxide,…

    The electrons to make cerium metal must come from somewhere. Reading the article, apparently microwave irradiation is enough to decompose cerium oxide into cerium metal and oxygen gas:

    CeO2 + microwaves => O2 (gas) + Ce(metal).

    The paper says that 0.2 mL of O2 is released per gram of CeO2. That equates to a conversion of 0.15% at STP.

    Abrupt release of O2 occurs at 200 C. However, further microwave heating does not produce further reduction or O2 evolution, even up to 750 C.

    Conventional heating does not produce O2 or elemental Ce, so the reaction may be induced by the oscillating electric field of the microwaves. Perhaps the reaction yield would maximize if the EM radiation were tuned to the Ce-O vibrational frequency.

    They used 2.45 GHz microwaves, but the Ce-O vibration is in the infrared centered near 24,000 GHz. Their 2.45 GHz is almost exactly 1/1000 of the center of the vibrational band, which may imply a weak resonant absorption. Maybe someone can do the experimental physics.

    The physical chemistry is interesting.

    But in any case, a 0.15% material conversion doesn’t seem to provide much industrial promise. Another interesting laboratory phenomenon at this point, touted in a climate change context. How unexpected is that?

    • The CeO2 is doped with Gadolinium, which must make some part of the chemical cycle more favourable. I don’t want to pay for the full study so I’m not sure what part the Gadolinium plays.

      • Gadolinium doping of CeO2 yields an electrolyte with high ionic conductivity at low temperature. For that reason, it has been widely used in fuel cells. This is just reversing that usage.

        While cerium is abundant, I’m not sure about gadolinium. Only about 400 tonnes of it are produced, worldwide – though that may just be a function of demand. It has some remarkable chemical, electromagnetic, and nuclear properties unique among the rare earths, but each application seems to require only trace amounts (“dopant” amounts). It’s used in nuclear magnetic resonance imaging, solid state lasers (optically pumped and diode), and an alloying material with metals to improve workability and oxidation resistance. Certain nuclear reactors use it as an emergency shutdown backup (due to its high neutron absorption cross-section), and as a burnable poison to exercise fine reactivity control over high-power density reactors. It is also being investigated for application in gadolinium-barium-copper oxide high-temperature superconductors. A truly fascinating element.

  7. Well, one would expect the abstract to at least mention how the theoretical neat energy output (in terms of the combustion specific enthalpy, in kWh/kg, of the H2 and O2 produced by this new water electrolysis method compares to the net energy input, also in kWh/kg, required to produce the H2 and O2 from water. If the overall efficiency of the proposed process is less than, say, 80%, the process offers no real improvement over common water electrolysis with a simple anode and cathode.

    Because this was not mentioned, one suspects the Spanish “breakthrough” is just another way to inefficiently consume electrical energy to produce hydrogen (and oxygen).

    BTW, to be completely correct and to balance mass flows in the above article’s lead-in process flow diagram, the box on the right needs to show an output of oxygen, assuming the cerium metal cannot oxidize/reduce a near-infinite amount of oxygen under microwave bombardment.

    • It seems that evidence of rigorous scholarship is no longer required by any journal if the article relates to AGW

    • currently many refineries produce hydrogen from natural gas in steam methane reformers(SMR). Related operations produce hydrogen from the chlor-alkali process for chlorine, reforming to produce olefins from CH2n hydrocarbons.

      Producing hydrogen with less energy and temperatures than the refineries use would probably be a useful reduction in energy usage.
      Until somebody actually produces at least an industrial sized pilot plant the lab trials are interesting chemistry. A working pilot plant would be an interesting new process- but it is highly unlikely hydrogen is going to replace batteries in electric vehicles any time soon.

  8. The giveaway is the yellow arrow labeled “Renewable Energy Powers the Microwave Generator”. It should read, “Magic Goes In Here.”

  9. If the energy input is drastically higher than the energy stored, you end up needing massive power plants to drive the reaction forward (at an industrial scale) and so you are back to either nuclear, natural gas, or intermittent power sources. This assumes you solve the engineering problems around needing purified water and catalyst poisoning.

    If you use intermittent energy sources and it takes twice the energy to create the hydrogen molecules as burning the hydrogen releases, then you need about 6 to 8 times the “green intermittent” capacity for the amount of stored energy produced. Oh, this is looking promising…(NOT).

    So this doesn’t appear to lead to a breakthrough in an economic sense. I didn’t even touch on the storage problem.

    Of course, for storage you could always take CO2 out of the air, remove the oxygen atoms and replace them with the hydrogen atoms producing good clean natural gas – at a huge cost. Then you combine natural gas atoms into longer chains you you get gasoline. That stores well (high energy density), and we already have all the infrastructure in place. Now if you could just remove the hugely expensive “produce hydrogen” step and find those gasoline molecules lying around in the ground somewhere you would really have a promising economic solution.

    • Yes, if only.

      But isn’t it totally unrealistic to think you could find very much hydrocarbon just lying around? 🙂

      The real problem with your idea is that if it worked, we would have dangerously inexpensive energy leading to a breakdown of government control and rampant freedom. Very irresponsible of you to propose this Robert. Shame!

  10. The last paragraph says it all: this is an expensive exercise in a lab that will not benefit your average Joe.

  11. When the cerium “de-oxygenates”, where does the free oxygen go and why wouldn’t the free oxygen re-oxygenate the cerium instead of extracting oxygen from the water?

  12. There’s plenty of alumin(i)um laying about that is branded as un-recyclable.
    There’s plenty of easily extracted sodium hydroxide (lye) laying about the former forest floors that “renewable” power has caused to be burned down, in the form of wood ash.
    Lye is also used to extract cerium, so you’re going to need some, anyway.
    Mixing lye, water, and alumin(i)m produces hydrogen gas and alumin(i)um hydroxide.
    Alumin(i)um hydroxide can be processed into usable alumin(i)um metal using the same industrial systems that process the raw ore. Plus a lot of electricity.
    The efficiency of the process should include the cost of collection for the materials.
    You’ll need plenty of cerium for your gas or whale oil lamps when the electricity runs out.
    Your cheap, green, free-trade, non-child-exploiting, third-world supporting hydrogen fuel cell is still the problem. Not the hydrogen.
    Then you have to get rid of the industrial heat from using your. Preferably no where near an official temperature recording weather station.
    (For the purposes of this missive, non-user’s of the spelling convention of the Queen’s English must be free to poke out their own (i)s where ever they feel necessary.)

  13. Typical efficiency of a microwave generator is 65%. So we lost 1/3 of the energy in the electricity that was generated via wind or solar, then we lose some more in the process to make hydrogen. Then we use more energy to compress the hydrogen to a pressure that makes sense for transportation. The high efficiency of the fuel cell (ignore its high cost and need for rare elements) cannot save the process. It is doomed by inefficiency.
    How does this even help?

    • One day when fossil fuel runs out this research might help with production of fossil fuel using nuclear power.

    • This is intended to be storage for wind an solar without having to back down nuclear and hydro sources. To meet the “zero by 2050” mandates, you will need to overbuild solar and wind capacity to supply energy when the wind don’t blow and sun don’t shine. Like on the order of 3-4 times. So rather than curtail the generation when the wind IS blowin’ and the sun IS shinin’ it is proposed to make and store hydrogen that can be used to recoup the energy. But, as has been pointed out, there are losses at every conversion step that cannot be avoided. One source I have seen indicates compressed hydrogen stored in caverns only returns 40% of the energy put into making and storing it. Is it worth it? You tell me.

  14. Todays version of a perpetual motion machine. As an engineer (Chemical) of 1971 vintage this stuff gets boring after the tenth time around what the h** are our universities teaching today, or are they teaching at all.

  15. Wind and solar generation have no ability to respond to load demand.
    This means they cannot be used to power the required microwave device unless it is supported by conventional electrical grid generation. Electrical equipment cannot operate on variable and intermittent energy sources. Period.
    This will end up being another load on the grid.

    • Demand and available renewable generation 24 hours ahead are VERY predictable though and resource such as pumped storage, hydro, demand response and grid scale batteries are there for sudden demand changes, frequency response, outages. so there’s no problem, is there?

      • Apparently with President Harris in the wings, it’s going to prove necessary to demonstrate the obvious financial realities to moronic true believers like griff, by collapsing society and producing mass misery and death.

        You can’t teach some children not to touch the hot stove. They must get burned to learn.

      • The problem is unnecessarily increasing the price of energy because you have been conditioned to fear that the same poisonous and polluting gas that you exhale will cause catastrophic climate change. You must realize that even if the IPCC was right about the effect of CO2, and they couldn’t be more wrong, inane policies like AOC’s New Green Disaster will have absolutely no effect on the planet’s average temperature. The ONLY effect will be to repress our economy.

        Why can’t you see the obvious problem here? Rather than take our wealth and redistribute it, getting us to destroy our own wealth under false pretenses serves the same goal.

      • Where was all this pumped storage, hydro and grid scale batteries during the recent California power outages? Grid scale batteries are a fools errand. All the grid scale batteries in the US will power LA for about 10 minutes.

  16. Why do they have to make it sound as just another overunity venture? Isn’t conversion of electricity to microwaves a process with a deplorably low efficiency?

    Or is is it that now burning hydrogen somehow produces overall more energy than it took to separate it from oxygen of water ?

  17. An example of repeated experiments expecting different results. The laws of thermodynamics bites again!

  18. The cyclical process proposed by the research team uses a soup of gadolinium-doped cerium oxide and water. Applying microwaves to the mixture electrochemically deoxygenates the cerium oxide, but when the microwaves stop, there’s a reaction with the water, and the cerium re-oxygenates and produces free hydrogen.

    Amazing the lengths we have to go to to replicate what has happened in plants at room temperature for 3 billion years.

    How many times more energy is consumed making hydrogen using exotic elements and microwaves, relative to hydrogen energy produced. 5? 10? 20?

    Here we report contactless H2 production via water electrolysis mediated by the microwave-triggered redox activation of solid-state ionic materials at low temperatures (<250 °C). Water was reduced via reaction with non-equilibrium gadolinium-doped CeO2 that was previously in situ electrochemically deoxygenated by the sole application of microwaves.

    Only 250 degrees C? Sounds like another cold fusion like scam to me.

    Hydrogen is a road to nowhere, as is green energy in general.

  19. I ain’t no materials scientist but I expect the CeO2 needs to be purified before use so the quoted $1800 per ton for raw oxide is likely very low.

  20. If I well understand the process, we produce hydrogen from WATER then we combine it with oxygen to produce WATER?
    But at the end will we have the same amount of water?

  21. Oh good Lord. Hydrogen is the present form of kookery that perpetual machines were back in the early 20th century.

  22. It won’t be long before the woke wizards come out opposing the process as an attack on water.
    A Save the Water Coalition will claim Hydrogen must be left in the water for the sake of water itself.

  23. Storing hydrogen is the problem. Let’s say someone buys a Hydrogen-powered car today. They keep it for several years… trade it in, it gets sold as a used car… driven for several years, finally, a dozen years from now, it’s given to a teenager as their first car. Would you want to park next to that rust bucket on a hot, sunny day?

  24. Let me guess, they only need $40 million from a state government or federal agency to scale it up to full production with lots of high-paying, green jobs.

  25. That process will be enormously expensive. Basically not much different from using sodium metal or some such. Handling of the cerium would be difficult and clunky, electrowinning it would be much worse than just single-step electrolysing water in a standard electrolyte.

    Pretty obvious these guys have no experience with real world process engineering or project financial analysis.

  26. Using hydrogen as a fuel seams to have become all the rage lately . There is a dispute between the use of “grey hydrogen” and “green hydrogen”. I didn’t realize hydrogen came in different colors !

  27. Meanwhile, in 1935 in U, Garrett patented in car produced hydrogen to fully power his vehcle using platinum and palladium eelctrodes o=in an electrolyte, and upgrading to a 12V systen. In 1998 Stan Meyer in US had patented hydrogen.. obtained by pulsed electronics to power his beach buggy using stainless steel electrodes. He was thne MURDERED. It’s OLD, suppressed tech.

    • So its old suppressed tech that you have unsurpressed…. or is it just old uneconomic tech that is still uneconomic?

  28. Despite the potential cost saving of this new catalyst, the green hydrogen produced by this generator is still very expensive, because of the cost of the renewable energy which is required to fuel the process

    But, but, but isn’t renewable energy free? griff has said so many times..

  29. Where was all this pumped storage, hydro and grid scale batteries during the recent California power outages? Grid scale batteries are a fools errand. All the grid scale batteries in the US will power LA for about 10 minutes.

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