How to properly treat potassium-iron oxide catalysts

Rotational spectroscopy has been used. Due to the small size, rotational transitions fall in the of the visible range for the H–H pairs, whereas for ordinary molecules they would be in the GHz (microwave) range.

• https://doi.org/10.1016/j.molstruc.2016.10.091
• https://doi.org/10.1016/j.molstruc.2018.06.116

Otherwise, laser time-of-flight has been most often used in the "Coulomb Explosion" experiments. When laser photons remove electrons from the H–H pairs (or larger fragments) in the ultra-dense clusters, the ions will repel each other by Coulomb repulsion, and by measuring the kinetic energy of the fragments it's possible to see that the bond energy was much higher than with ordinary molecules.

A more accessible method would be observing nuclear reactions, since it is argued that they are easily possible only if the hydrogen atoms are at a very close distance with each other.

I think all of these methods are outside the scope of this thread, which was initially started because information on the catalysts used for UDH production wasn't too well known. With the recent publication of a paper dedicated on the catalysts by Holmlid et al., it has probably run its course.

milton

It hasn't changed, in that it indeed is the active compound of iron-oxide styrene catalysts and likely also other alkali-promoted iron oxide catalyst types. It could perhaps be added that the decomposition of this compound at higher temperatures (>800–900 °C) and/or vacuum conditions yields a potassium-deficient ferrite phase (K₂Fe₂₂O₃₄, also known as potassium β-ferrite) from which potassium loss should be even faster, which could in turn lead to faster potassium alkali Rydberg matter formation. This potassium loss is industrially disadvantageous, so it is usually avoided with stabilizers (oxide additives).

https://doi.org/10.1016/j.ijhydene.2021.02.221

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[...] The use of additives to delay the loss of the promoter may give further options [87,88]. One of the strategies to stabilize alkali in the mixed oxides is to hinder the alkali ion bulk diffusion, as observed for Cr doping of β-ferrite. This strategy may not be so useful for H(0) formation, since the promoter needs to be able to diffuse and desorb for Rydberg states and Rydberg matter to be formed.

https://doi.org/10.1006/jcat.2002.3725 (2002)

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Abstract: Thermal desorption of potassium ions and atoms from K-doped iron oxides (Fe3O4, Fe2O3) and potassium ferrites (KFeO2, K2Fe22O34) that are the principal phases of the iron oxide catalysts for dehydrogenetion of ethylbenzene to styrene was investigated. From the Arrhenius plots the activation energies for desorption of K and K+ were determined in the process temperature range for each of the phases. Based on these results the desorption energies obtained previously for the commercial styrene catalysts were reinterpreted and the K storage and release phases were explicitly identified. The results were discussed in terms of a surface stability diagram. It was shown that in the active state of the catalyst the K2Fe22O34 component is responsible for excessive potassium release. The proposed optimal morphology of the catalyst grain consists of a core K2Fe22O34 surrounded by a compact shell of active KFeO2, while a core and cracked-shell model was adapted to account for the potassium desorption data from the real catalysts.

Key figures from the above paper:

Another related more recent publication on the topic: https://doi.org/10.1016/j.jcat.2007.02.009

In a 2006 paper by Alpermann and Holmlid it was inferred that Rydberg matter formation was more intense from potassium diffusing from graphite patches and this K₂Fe₂₂O₃₄ phase: https://doi.org/10.1016/j.saa.2006.09.003

JL123

Thanks, although as I mentioned earlier, with the recent publication of a paper on the catalysts for ultra-dense hydrogen production by Holmlid, Kotarba, Stelmachowski, this thread has probably run it course.

Some authors, e.g. Muhler et al. in https://doi.org/10.1016/0021-9517(90)90003-3 , do indeed describe the final inactive state of iron oxide styrene catalysts as a "spatially-disintegrated" core-shell structure, where the core would be enriched with segregated KOH.

I don't know if this is entirely applicable for the experiments by Holmlid et al. where steam is not introduced and thus KOH would not form, but it has been sometimes pointed out that the loss of promoter (K) from the catalyst (due to diffusion and desorption by heating in a vacuum) eventually leads to deactivation and inability to form ultra-dense hydrogen and Rydberg matter, e.g. in https://doi.org/10.1007/s10876-011-0387-1 :

Looking back at this thread, it looks like some of the larger-size animations and photos I posted in the past are not working anymore. I did not delete them; I think they got lost during a forum software update, after stricter image attachment size restrictions were introduced. Can they be recovered, barty ?

This patent recently referenced by Bob Greenyer in a video elsewhere, reminds me of the process I explored with steel sheets and concentrated KOH solutions, only at the time I didn't know whether the method would be useful.

The patent is about bringing in contact steel surfaces with alkali-containing compounds (in particular KOH or NaOH) in a closed cell, increasing temperatures above 300 °C or especially in the 500–700 °C range and admitting steam.

The surfaces treated in this way would form a "higher-order alkali metal-transition metal oxide having high water absorption performance, hydrogen storage performance, fuel cell electrode performance and nuclear reaction induction performance."

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Abstract

PROBLEM TO BE SOLVED: To provide a multifunctional and low-cost higher alkali metal-transition metal oxide.SOLUTION: The inside of a stainless steel- or iron-made reaction cell 1 is filled with an oxygen-free atmosphere, an alkali metal-containing compound such as NaOH or KTiOis placed therein as a reactant, fine particles of the reactant are scattered therein by heating the reaction cell 1 to 500-700°C, a higher alkali metal-transition metal oxide film is generated on an inside wall of the reaction cell 1 by supplying steam to the reaction cell 1, and the oxide film is used as a moisture absorbent, a hydrogen storage material, an electrode material of a fuel cell, and a nuclear reaction inducer.

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Claims

• 1) A stainless steel or iron material and a reactant are installed in an oxygen-free atmosphere free from oxygen in the air, and the atmosphere is heated to disperse fine particles of the reactant into the atmosphere. A high-order alkali metal-transition metal oxide formed on the surface of a stainless steel or iron material.
  • 2) The high-order alkali metal-transition metal oxidation according to claim 1, wherein the stainless steel is austenitic stainless steel containing nickel, and the reactant is sodium hydroxide (NaOH) or potassium hydroxide (KOH). object.
  • 3) The high-order alkali metal-transition metal oxide according to claim 1 or 2, wherein the oxygen-free atmosphere is heated to 500 to 700 ° C or higher.
  • 4) The high-order alkali metal-transition metal oxide according to any one of claims 1 to 3, wherein the high-order alkali metal-transition metal oxide is formed as a thin film while maintaining the oxygen-free atmosphere at a pressure lower than 1 atm while being sucked with a vacuum pump.

In practice, this does not appear to require very high temperatures or a closed cell. Ferritic steel or iron work at lower temperatures than stainless steel as suggested here, however.

As already mentioned numerous times, the obtained surfaces would turn olive green and easily absorb water, decomposing in the process. I posted photos of this in the past, but either they got lost or I never uploaded some showing the initial clean steel piece, so here are a few more.

Also with ferritic stainless steel:

After a more detailed read, it seems they are attributing the claimed properties to a slightly different alkali-metal oxide compound derived from the initial one formed by reacting steel with KOH/NaOH and steam. The translated version of the actually published patent (JP6059918B2) has somewhat more specific claims to reflect this (compare with the ones I posted above).

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Claims

• 1) A reactive agent made of stainless steel or iron and sodium hydroxide or potassium hydroxide is installed in an oxygen-free atmosphere free from oxygen in the air, and the atmosphere is heated to disperse the fine particles of the reactant into the atmosphere. A method for producing an electrode material for a fuel cell, wherein water vapor is supplied into the atmosphere to form an oxide film on the surface of the stainless steel or iron material.
  • 2) The oxide film according to claim 1, wherein the oxide film is at least one of Na₃Fe₅O₇, K₃Fe₅O₉, and Na_xFe_yCr_zO_w (where x, y, z, and w are integers). Manufacturing method of electrode material of fuel cell.
  • 3) The method for producing an electrode material for a fuel cell according to claim 1 or 2, wherein the inside of the oxygen-free atmosphere is heated to 500 to 700 ° C or higher.
  • 4) The method for producing an electrode material for a fuel cell according to claim 1, wherein the oxygen-free atmosphere is formed as a thin film while being maintained at a pressure lower than 1 atm while being sucked by a vacuum pump.

From the text (a translation, so not 100% clear or accurate) it appears that further reacting the intermediate compound formed (NaFeO₂ or KFeO₂) with steam at presumably elevated temperature and the (underlying) steel surface would form those compounds, with seemingly slight differences depending on the partial pressure of oxygen in the reaction environment.

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[...] Furthermore, this NaFeO₂ reacts with water vapor and iron (Fe),

3NaFeO₂ + 2Fe + 3H₂O → Na₃Fe₅O₉ + 3H₂ (3)

A higher order alkali metal-iron oxide (9) is produced. At this time, alkali metal-iron oxides such as Na₃Fe₅O₈, Na₄Fe₆O₁₁, and Na₅FeO₄ are generated due to the difference in oxygen partial pressure.

I think this would basically occur almost at the same time as that of the formation of the precursor compound, since reaction conditions are about the same.

Just wanted to add that the authors of the previously linked patent justify their claim of the material and procedure inducing nuclear reactions due to:

1. Excess hydrogen production relatively to the admitted water. They write that according to the final chemical reaction equation 1.25 moles of hydrogen per mole of water should be produced, but they see more than 1.5;
2. Neutrons and gamma rays detected during the reaction (no other details provided);
3. Formation of new elements on the inner walls of the (steel) contained used for the reaction (i.e. transmutation) like Al and Zn;
4. Hydrogen and gases of mass 16 and 27 detected with a mass analyzer (RGA?) when a certain active compound (K₂TIO₃) was used without admitting steam or hydrogen, but not O₂ (mass 32);
5. Hydrogen outlet temperature decreasing by 200 °C during the reaction, which the authors couldn't explain with ordinary chemical reactions.

There is more patent documentation on the USPTO Global Dossier, all of which in original and translated form, but I haven't noticed yet anything else of interest: https://globaldossier.uspto.go…ils/JP/2012188969/A/99822

It seems anyway that in the end the patent is mostly about the reaction of NaOH/KOH with steam on the steel walls, forming this alkali-metal oxide and hydrogen as a result. As it's a form of accelerated corrosion, and the patent mentions that the oxide film formed peels off, allowing the formation of a new film (which will further peel off, and so on), eventually the steel container or other steel parts put inside of it would be eventually destroyed, as seemingly implied also in the (translated) description.

Quote from Google Translate

[...]When these films are reacted for a long time, they are formed in a multilayer on the iron or stainless steel surface as shown in FIG. 2, and when the first oxide film l1 formed becomes a predetermined thickness, they peel off from the inner wall and a new inner wall surface is exposed, the next second oxide film l2 further the second oxide film l2 peels off to form the next third oxide film l3. Then, fine particles are scattered from the oxide film l (l1, l 2, l3) surface at 500 to 700 ° C., and the reactivity between these fine particles and water vapor is remarkably high.

This should not be difficult to test (requiring a stainless steel tube/container, NaOH/KOH and steam) but the nuclear products and transmutations will require dedicated equipment.

Rob Woudenberg

Yes, it appears that one of the inventors (Yasuo Ishikawa) has a few patent applications written with Tadahiko Mizuno as a co-inventor, for example:

JP2018036275A - Nuclear fusion reaction method and nuclear fusion reaction device - Google Patents

JP2014037996A - Nuclear fusion reaction method - Google Patents

JP2013112576A - Method and apparatus for generating hydrogen - Google Patents

But one the main reasons for my interest in the patent linked earlier is that I think it's quite related to the Fe-K oxide catalysts described in this thread and their active phases.

It's also possible that the process of forming such phases from Fe, NaOH/KOH and steam may form at least transiently particularly reactive species, which could promote the observation of anomalous results. In some crude tests with small steel plates treated similarly to what the patent suggests I observed for example that pre-deposited soot/carbon is very readily combusted in particular while such green-colored phases are formed.

Quote from can

It's also possible that the process of forming such phases from Fe, NaOH/KOH and steam may form at least transiently particularly reactive species, which could promote the observation of anomalous results. In some crude tests with small steel plates treated similarly to what the patent suggests I observed for example that pre-deposited soot/carbon is very readily combusted in particular while such green-colored phases are formed.

I made some photos at the time. The steel plate (already treated with KOH solution and green-looking, but dry) below was covered with candle soot. I then dropped some KOH solution and let it evaporate from the heat of a hot Kanthal wire (also treated with KOH: it's yellow-green because of this) at close distance. Surface temperature on the plate was about 300 °C at most. As the green iron-potassium oxide compound re-formed, most of the soot disappeared within a short period.

I'm aware that carbon gasification is a known process, but this seems to happen fast and at low temperature as this kind of active surface forms.