Fraunhofer ISI zerlegt Wasserstoff-Mythen und zeigt die Grenzen

Empfehlenswert! Wer glaubt, das Wasserstoff die beste, machbare Lösung für die sogenannte Energiewende ist irrt sich vielleicht!

"Wasserstoff gilt vielen als Schlüssel zur Klimaneutralität. Er soll Flugzeuge antreiben, Häuser heizen und die Industrie retten. Doch wie realistisch sind diese Szenarien? Das Fraunhofer-Institut für System- und Innovationsforschung (ISI) hat in einem umfassenden Meta-Faktencheck mehr als 100 Studien ausgewertet.

Das Ergebnis ist eine deutliche Warnung vor zu viel Euphorie. Wasserstoff ist eine wertvolle Ressource, aber er ist kein Allheilmittel. Wo die Grenzen liegen und warum wir uns bei der Infrastruktur konzentrieren müssen, zeigt die aktuelle Analyse. ...

Der Befund ist klar: Wasserstoff wird eine wichtige Rolle spielen, aber er wird das Energiesystem nicht dominieren. Er ersetzt Strom nicht, sondern ergänzt ihn in bestimmten Anwendungen. Ein flächendeckender Einsatz, wie er häufig diskutiert wird, ist weder wirtschaftlich noch energetisch sinnvoll. ...

Für die Herstellung von Wasserstoff werden je nach Verfahren rund 50 bis 60 kWh Strom pro Kilogramm benötigt. Eine breite Nutzung würde den Strombedarf des Energiesystems erheblich erhöhen.

Hinzu kommen weitere Verluste entlang der Kette:

• Erzeugung: Elektrolyse reduziert den Wirkungsgrad deutlich
• Logistik: Kompression oder Verflüssigung kostet zusätzliche Energie
• Anwendung: In Brennstoffzellen oder bei der Verbrennung gehen weitere Anteile verloren

..."

Fraunhofer ISI zerlegt Wasserstoff-Mythen und zeigt die Grenzen

Wasserstoff: Meta-Faktencheck liefert Antworten auf zentrale Fragen

New experiments suggest Earth's core contains up to 9-45 oceans' worth of hydrogen

Amazing stuff! This estimate presents an unusually huge range! They need to measure this again! 😊

From the abstract:

"Earth’s core has long been speculated to be the largest reservoir of hydrogen (H) on the planet. However, current estimates of its H content involve substantial uncertainties, due to the challenge of quantifying H under extreme conditions.

Here, we perform superliquidus metal-silicate partitioning experiments on H using laser-heated diamond anvil cells, and combine it with atom probe tomography.

The direct observation of H at silicon- and oxygen-rich nanostructures in the iron alloy indicates coupled sequestration of silicon, oxygen and hydrogen into Earth’s core during its formation. With the observed molar Si/H ratio close to unity, Earth’s core is estimated to contain 0.07-0.36 wt.% H, equivalent to 9-45 oceans of water. Such an amount would require the Earth to obtain the majority of its water from the main stages of terrestrial accretion, instead of through comets during late addition."

New experiments suggest Earth's core contains up to 45 oceans' worth of hydrogen

Experimental quantification of hydrogen content in the Earth’s core (open access)

Fig. 4: Metal-silicate partition coefficient of hydrogen inferred from varying H/Si ratios in the metal.

Pinning down protons in water — a basic science success story

Amazing stuff! Towards hydrogen power!

"The movement of protons through electrically charged water is one of the most fundamental processes in chemistry. It is evident in everything from eyesight to energy storage to rocket fuel — and scientists have known about it for more than 200 years.

But no one has ever seen it happen. Or precisely measured it on a microscopic scale.

Now, [researchers] ... — for the first time — set benchmarks for how long it takes protons to move through six charged water molecules. The discovery, made possible with a highly customized mass spectrometer that has taken years to refine, could have far-reaching applications for researchers in years to come. ..."

Unfortunately, the link to the research paper in the article below is broken. My guess is that this is the paper titled "Microcanonical Kinetics of Water-Mediated, Long Range Proton Transfer in Microhydrated 4-Aminobenzoic Acid". Google Scholar can not find this paper, but Google search found it.

From the abstract:

"Editor’s summary

Proton transfer is perhaps the most fundamental chemical reaction, underlying numerous more complex transformations in both biochemical and synthetic systems. The process often involves a network of numerous water molecules. To home in on the details in a well-controlled context, Rana et al. studied interconversion of two protonated isomers, or protomers, of 4-aminobenzoic acid in small water clusters. By measuring the kinetics of proton migration between nitrogen and oxygen sites with well-resolved spectroscopic signatures, the authors were able to establish precise benchmarks for future modeling. ...

Abstract

Isolated cluster systems can help to elucidate the molecular level description of water-mediated proton transfer. Protonation of neutral 4-aminobenzoic acid (4ABA) occurs at the acid (O-protomer) and amine (N-protomer) functionalities, yielding two distinct species with relative energies dependent on the degree of hydration.

Here, we measured the rates of intramolecular proton transfer in 4ABAH+·(H2O)6 ions upon protomer-selective vibrational excitation of initially cold (6 K) cluster ions isolated in a cryogenic ion trap. Interconversion rates were observed on the microsecond time scale.

These results quantify the kinetics of proton transfers in the context of a closed, finite system at well-defined internal energies and therefore provide experimental benchmarks for theoretical efforts that are being developed to treat relatively slow, highly cooperative solvent-mediated chemical processes."

Pinning down protons in water — a basic science success story | Yale News "In a new study, ... team set measurable parameters on the movement of protons in water — shedding new light on one of basic science’s most enduring enigmas."

Microcanonical kinetics of water-mediated proton transfer in microhydrated 4-aminobenzoic acid (no public access)

Payten Harville, left, Abhijit Rana, and Mark Johnson (three of the authors) operate a customized mass spectrometer that has been adapted to enable multiple interactions with carefully timed pulses of laser light.

A low-cost catalytic cycle could advance the separation, storage and transportation of hydrogen

Good news! However, would it not be better to generate hydrogen from water?

Always remember the Hindenburg disaster of 1937!

"... Despite its potential for various real-world applications, hydrogen is often expensive to produce, store and safely transport to desired locations. Moreover, before it can be used, it typically needs to be purified, as hydrogen produced industrially is typically mixed with other gases, such as carbon monoxide (CO), carbon dioxide (CO₂), nitrogen (N₂) and light hydrocarbons. ...

Researchers ... recently devised a new strategy to separate hydrogen from impurities at low temperatures, while also enabling its safe storage and transportation. Their proposed method ... relies on a reversible chemical reaction between two organic compounds that act as hydrogen carriers, enabling the reversible absorption and release of hydrogen.  ...

The strategy they proposed relies on a low-cost catalytic cycle, which involves the reversible interconversion of the compounds γ-butyrolactone (GBL) and 1,4-butanediol (BDO). ...

"Using crude hydrogen feeds with over 50 vol.% impurities, GBL is hydrogenated to BDO at 170 oC, achieving >99.2% H2-to-BDO selectivity while suppressing side reactions," ... "The hydrogen-rich BDO can then be safely stored and transported using existing liquid fuel infrastructure. Upon demand, catalytic dehydrogenation regenerates GBL and releases high-purity hydrogen (>99.998%), free of COx impurities." ...

used an inexpensive copper-based catalyst to capture hydrogen from impure industrial gas streams and store it in BDO, a cheap and safe oil-like liquid. Notably, this liquid can be transported using the same tanks, pipelines and trucks that are currently used to transport other fuels. When it reaches its destination, the hydrogen stored in the liquid can be easily released with high purity. ...

"A key advantage of our strategy is that both the catalyst and the liquid organic hydrogen carriers or LOHC (GBL/BDO) are abundant and inexpensive," ...

"Moreover, hydrogen capture and storage occur in a single step, simplifying the overall system. Our approach is safe and scalable ..."

From the abstract:

"Industrially, hydrogen production often relies on carbon-based resources, necessitating the separation of hydrogen from impurities such as CO, CO2, hydrocarbons and N2. Traditional purification methods involve complicated and energy-intensive sequential conversion and removal of these impurities.

Here we introduce a reversible catalytic cycle based on the interconversion between γ-butyrolactone and 1,4-butanediol over an inverse Al2O3/Cu catalyst, enabling efficient hydrogen separation and storage from crude hydrogen feeds. This process could transform crude hydrogen feeds containing over 50% impurities into pure hydrogen at low temperature.

The low impurity affinity and high dispersion of inverse Al2O3/Cu facilitate catalytic crude and waste hydrogen separations previously considered unachievable. This approach avoids the need for expensive pressure swing adsorption or membrane systems in liquid organic hydrogen carriers, showing great potential for large-scale applications in crude hydrogen or industrial tail gas utilization processes. By providing a low-risk, energy-efficient alternative, this strategy supports the global transition from grey/blue hydrogen to green hydrogen."

A low-cost catalytic cycle could advance the separation, storage and transportation of hydrogen

A catalytic cycle that enables crude hydrogen separation, storage and transportation (no public access)

Magnet-cooled crystals could help liquefy hydrogen fuel based on the giant magnetocaloric effect

Good news! A "giant" effect? 😊

Still, the million dollar question is how safe will be the handling of hydrogen overall? Remember, e.g. the Hindenburg disaster of 1937!

"Researchers have made a material capable of cooling substances down to -253°C – enough to liquefy hydrogen – using magnets.

They say their research ... could provide a cheaper and more sustainable way to supercool hydrogen fuel for storage and transport.

The researchers tapped into the “magnetocaloric effect”: applying magnetic fields to certain substances can change their temperature. ...

The pink crystals could cool to 20 Kelvin, or -253°C. Just 20°C above absolute zero, this is cool enough to prompt the condensation of hydrogen, rendering it a liquid. ..."

"... Blake used magnetocaloric cooling to reach 20°K, cold enough to liquify hydrogen. This has been done before, but only with materials containing rare-earth metals. ..."

From the abstract:

"Magnetic refrigeration, which utilizes the magnetocaloric effect, can provide a viable alternative to the ubiquitous vapor compression or Joule-Thompson expansion methods of refrigeration. For applications such as hydrogen gas liquefaction, the development of magnetocaloric materials that perform well in moderate magnetic fields without using rare-earth elements is highly desirable. Here we present a thorough investigation of the structural and magnetocaloric properties of a novel layered organic-inorganic hybrid coordination polymer Co4(OH)6(SO4)2[enH2] (enH2 = ethylenediammonium). Heat capacity, magnetometry and direct adiabatic temperature change measurements using pulsed magnetic fields reveal a field-dependent ferromagnetic second-order phase transition at 10 K << 15 K. Near the hydrogen liquefaction temperature and in a magnetic field change of 1 T, a large maximum value of the magnetic entropy change,  = − 6.31 J kg−1 K−1, and an adiabatic temperature change, 

 = 1.98 K, are observed. These values are exceptional for rare-earth-free materials and competitive with many rare-earth-containing alloys that have been proposed for magnetic cooling around the hydrogen liquefaction range."

Magnet-cooled crystals could help liquefy hydrogen fuel

Magnetocaloric cooling method produces liquid hydrogen using environmentally friendly technology

Giant magnetocaloric effect in a rare-earth-free layered coordination polymer at liquid hydrogen temperatures (open access)

Fig. 1: Structure of Co4(OH)6(SO4)2[enH2].

Laser pulses extract hydrogen from ammonia dissolved in water without catalyst

This seems to be an interesting approach, but it may not be practical!

At least this article below mentions how dangerous hydrogen is. Compression and storage are other issues with hydrogen.

"Laser pulses that can shred ammonia molecules dissolved in water may offer a way to generate hydrogen gas without using heat, pressure, or catalysts ... The proof-of-principle work by researchers at Sun Yat-sen University demonstrates an unusual way to exploit ammonia as a carrier for green hydrogen, an idea that is quickly gaining traction in many industries. ...

Delivering that hydrogen to where it is needed is tricky and expensive, not least because it is explosive and flammable. It can be transported as a highly compressed gas or as a liquid at –253 °C, both of which are relatively expensive options for a fuel. ...
However, ... that the energy that would be gained from burning the hydrogen is less than half the amount of energy the laser uses to produce it, making it impractical for industrial use. ...
To overcome this drawback, the ... researchers suggest that their new process could instead be powered by a solar-pumped laser. ..."

From the abstract:

"As a good carrier of hydrogen, ammonia–water has been employed to extract hydrogen in many ways. Here, we demonstrate a simple, green, ultrafast, and highly efficient method for hydrogen extraction from ammonia–water by laser bubbling in liquids (LBL) at room temperature and ambient pressure without catalyst. A maximum apparent yield of 33.7 mmol/h and a real yield of 93.6 mol/h were realized in a small operating space, which were far higher than the yields of most hydrogen evolution reactions from ammonia–water under ambient conditions. We also established that laser-induced cavitation bubbles generated a transient high temperature, which enabled a very suitable environment for hydrogen extraction from ammonia–water. The laser used here can serve as a demonstration of potentially solar-pumped catalyst-free hydrogen extraction and other chemical synthesis. We anticipate that the LBL technique will open unprecedented opportunities to produce chemicals."

Lasers liberate hydrogen from ammonia water

Efficient and Rapid Hydrogen Extraction from Ammonia–Water via Laser Under Ambient Conditions without Catalyst (no public access)

Low-emissions flash method upcycles waste plastic into "free" hydrogen

Good news! Dedicated to all those who suffer from plastophobia! 😊

"Researchers have used a low-emissions method to harvest hydrogen and graphene from waste plastics. They say it not only solves environmental problems like plastic pollution and greenhouse gas production, but the value of the graphene by-product could offset the costs of producing hydrogen. ...
“In this work, we converted waste plastics – including mixed waste plastics that don’t have to be sorted by type or washed – into high-yield hydrogen gas and high-value graphene,” ...
In the current study, the researchers exposed plastic waste to rapid flash Joule heating for about four seconds. Raising the temperature up to 3,100 kelvin vaporizes the hydrogen present in the plastic, leaving behind graphene, a light, durable material comprised of a single layer of carbon atoms. ...

“We know that polyethylene, for example, is made of 86% carbon and 14% hydrogen, and we demonstrated that we are able to recover up to 68% of that atomic hydrogen as gas with a 94% purity,” ..."

From the abstract:

"Hydrogen gas (H2) is the primary storable fuel for pollution-free energy [???] production, with over 90 million tonnes used globally per year. More than 95% of H2 is synthesized through metal-catalyzed steam methane reforming that produces 11 tonnes of CO2 per tonne H2. “Green H2” from water electrolysis using renewable energy evolves no CO2, but costs 2–3x more, making it presently economically unviable. Here  we report catalyst-free conversion of waste plastic into clean H2 along with high purity graphene. The scalable procedure evolves no CO2 when deconstructing polyolefins and produces H2 in purities up to 94% at high mass yields. Sale of graphene byproduct at just 5% of its current value yields H2 production at negative cost. Life-cycle assessment demonstrates a 39–84% reduction in emissions compared to other H2 production methods, suggesting the flash H2 process to be an economically viable, clean H2 production route."

Low-emissions flash method upcycles waste plastic into "free" hydrogen

Making hydrogen from waste plastic could pay for itself  (primary news source) Graphene by-product offsets ‘flash’ hydrogen production costs, Rice study finds

Here is a previous article about a previous study about their rapid flash Joule heating method: Potential for profits gives Rice lab’s plastic waste project promise ‘Flash Joule’ technique efficiently turns would-be pollution into valuable nanomaterials

Synthesis of Clean Hydrogen Gas from Waste Plastic at Zero Net Cost (no public access)

Scanning electron microscope (SEM) image of layered stacks of nano-scale flash graphene sheets formed from waste plastic.

Yeast thriving in hydrogen hints at possibility of life on exoplanets

Amazing stuff! We are not alone!

Yeast thriving in hydrogen hints at possibility of life on exoplanets | Research | Chemistry World: First demonstration of non-adapted microorganisms growing in 100% H2 shows that life could exist even under seemingly hostile conditions

Planets with hydrogen-rich atmospheres could harbor life | Science News Lab experiments show that yeast and E. coli survive and reproduce in hydrogen-rich conditions

Superconductivity Up To 200 Degrees Celsius

Posted: 8/31/2019

“The newly predicted superconductor, a compound of hydrogen, magnesium and lithium, ... must be squeezed to extremely high pressure, nearly 2.5 million times the pressure of Earth’s atmosphere” (S1; emphasis added)

Here is the abbreviated abstract of the research paper (S2; emphasis added):

“The recent theory-orientated discovery of record high-temperature superconductivity (Tc∼250K) in sodalite like clathrate LaH10 is an important advance toward room-temperature superconductors. Here, we identify an alternative clathrate structure in ternary Li2MgH16 with a remarkably high estimated Tc of ∼473K at 250 GPa, which may allow us to obtain room-temperature or even higher-temperature superconductivity. ... The extra electrons introduced break up the H2 molecules, increasing the amount of atomic hydrogen … which is necessary for stabilizing the clathrate structure or other high-Tc structures. Our results provide a viable strategy for tuning the superconductivity of hydrogen-rich hydrides by donating electrons to hydrides via metal doping. ...”

But keep in mind, this appears to be so far only a theoretically calculated, simulated kind of superconductor. Can a superconductor like this (hydrogen rich compound; high pressure; electron doping) ever be mass produced.

Sources (S):

1. A predicted superconductor might work at a record-breaking 200° Celsius The hydrogen-rich material would still need to be squeezed to extremely high pressures (8/30/19)
2. Route to a Superconducting Phase above Room Temperature in Electron-Doped Hydride Compounds under High Pressure (8/26/19)