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How to get the right catalyst?

Written by Robert Greenyer on .

There is a lot of debate around what catalysts lead to successful LENR, one compound that seams to crop up again and again is various Iron Oxides - Bob Higgins has talked about the importance of this and has even published a way to process Nickel and Iron Oxides into what may be part of an effective LENR fuel mix.

With respect to the recent report by Ólafsson and Holmlid, Ecco mentioned this

"Holmlid used Shell 105 catalyst (Fe2O3-K based with >8% K content) - and only that (!!) - as an ultra-dense Rydberg state Deuterium generator because it's convenient to use, cheap and apparently because it works out of the box without further treatment (as also confirmed by Sveinn Ólafsson on LENR-Forum)."

So there is an off-the shelf catalyst that just works for production of ultra-dense Rydberg state Deuterium - well that is all very well - but how does that teach us anything about what goes into making a catalyst and why?

Well, this paper from early 2010 (before Rossi's first demo), written by 
Sreelekha Benny, Department of Chemistry, University College London in the Johnson Matthey Technology Centre has a great discussion on Iron Oxide catalysts and dopants, note that Parkhomov had nearly 3.7% Mn and over 20% Al in his fuel by atom%

Catalyst Study

From page 102
Doping magnetite with Al3+ produces the most negative defect energy of -4.63eV but from page 104 you can see that Mn3+ has the lowest solution energy.

From page 111
Look at where Al and Mn cation dopants sit on the plot

From page 116
"It has been reported that Al2O3 exists as a separate phase in the hematite bulk with a high thermal stability and that the catalytic activity increases with temperature"

From page 122-123
"The ions with similar radii as Fe3+ such as Cr3+, Mn3+, V3+ and Ti3+ possess similar solution energies and they form solid solutions in the bulk of hematite, whereas Al3+ is soluble in the surface. The bigger ions, Y3+ and La3+ would be expected to form separate oxide layers." 

Note that Al3+ is the only dopant soluble in the surface.

Again, from page 123
"Finally by comparing all these energies, Al3+, Mn3+ and Ti3+ could be suitable alternatives for Cr3+. However, Ti3+ is not considered due to its anticipated electron transfer with Fe3+ and a tendency to remain in the Ti4+ oxidation state. As Al3+ is harmless and the behaviour of Mn3+ is similar to Cr3+, these two dopants have been chosen for further study."

So, the suggestion by this author is to only study Al3+ and Mn3+ which as said above, is both present in Parkhomov fuel

In the next section they compare these two as dopants with the problem child Cr, the stability and the effect of magnetic fuel in ferro and para magnetic states.

Very interestingly, on page 149
"To conclude this part, the Fe-Al-O solid solution is meta-stable with respect to the separated phases and the mixed solution will only exists at very high temperature. The calculated results verify the results reported by some authors18,21 that the solution is stable above 1600K."

That's 1326.85ºC

From page 151

"In the preparation of active WGS catalysts, the precursor material, hematite is reduced to magnetite." 

Could the initial slow release of H2 from LiAlH4 perform this function if hematite is included?

From page 174
"The Al3+ - doped system has the most disorder at low temperature, while the Mn3+- doped system shows the most extensive disorder at high temperatures."

From page 202
"Aluminium shows a particular tendency to promote oxygen vacancies even if they are in the tetrahedral sites, suggesting that the presence of aluminium will enhance the surface [catalytic] reactivity by producing oxygen vacancies more easily."

From Page 203
"Addition of impurities affects the stability of the surface; for example, the presence of aluminium and divalent manganese increases the surface stability, whereas, chromium, aluminium and manganese in their trivalent oxidation state should make the surface more active by promoting oxygen vacancy formation. Aluminium-doped magnetite leads to highly stable surface encouraging large surface area. "

From page 207
"It is generally accepted that the role of chromium in the WGS reaction is to prevent sintering, increase the surface area of the catalyst and suppress the over-reduction of the active catalyst" 

Could Aluminium play a similar anti-sintering role on Nickel also?

In fact, could any of the above work in a similar way with Nickel, but doesn't that take us back to Raney-Nickel?

And with the addition of Lithium, what compounds and structures are made with Iron Oxide, manganese and Aluminium - maybe the battery business has the answers?

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0 #67 Image edit 2018-05-08 10:22
Incredible! This blog looks exactly like my old one!
It's on a completely different subject but it has pretty much the
same layout and design. Great choice of colors!
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0 #65 EveretteSmall 2018-02-09 16:01
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0 #64 axil 2015-10-08 19:17
@Ecco

You said:

"What if Lithium, as a penetrating corrosive agent (especially in the case of Nickel), is accelerating the embrittlement/c orrosion process so that eventually, yet at a quicker rate than normal, the right nanoscale structures can appear on the metal?"

This is a good observation. This fits in with the fuel preprocessing that Rossi has done as seen in the Lugano test. The 100 micron nickel particle that the preprocess method produces is covered with lithium throughout its entire surface area. During preprocessing, the application of lithium at high temperatures might erode the surface of the nickel particle(S) to form nanocavities as happens in palladium at high hydrogen loading levels. Maybe the crack idea of Ed Storms holds merit.

Parkhomov uses a low quality powder with lots of carbon on the surface. Lithium processing might erode that carbon and leave nano cavities on the surface of the nickel powder as occurs in palladium at high hydrogen loading. Maybe the Russian nickel powder is good because it is so poor in production. A powder with abundant carbon content might be the best type of powder to use.

Furthermore, the surface of the nickel powder becomes saturated with lithium to the point where lithium is no longer consumed in nickel alloying. When the reaction begins with LAH, lithium is no longer consumed and remains free and available for the LENR reaction to use.

Another thing that could be happening in the high carbon surface preprocessing of Russian nickel powder is that lithium carbide is formed on the surface of the powder. These lithium compound might produce both lithium and hydrogen Rydberg matter during the reaction stage through a desorption process.
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0 #63 axil 2015-10-07 06:14
I also found this article that explains how the Rydberg matter catalysts work.

Maybe someone might be kind enough to explain this article to me in simple terms.


First-principles studies on K-promoted porous iron oxide catalysts

sciencedirect.com/science/article/pii/S2352214315000106
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0 #62 axil 2015-10-05 19:39
High temperature lithium corrosion seems to be presenting a major problem in material engineering of the LENR ceramic tube reactor. Using a metal tube is problematical because lithium dissolves metals through a voracious alloying process and ceramics are short lived because lithium readily combines with oxygen, nitrogen, and carbon until a saturation point is reached. When a lot of lithium is needed that saturation point might not occur until after the ceramic tube has failed.

I would bet that Rossi is trying to find a lithium resistant material for the tube of his new the E-Cat-X reactor. Very high operating temperatures that the E-Cat X is running at makes lithium vapor corrosion intense.

One solution to this very difficult high temperature corrosion problem might be to uses a ceramic that contains lithium that has already reached the saturation level. "LITHIUM DISILICATE GLASS" might be resistant to lithium corrosion. A test of this material that is an alternative ceramic material used in dental crowns might be worth testing for high temperature lithium corrosion resistance.

sgiglass.com/ is a supplier and fabricator of this material. Such a fabricator might be tasked to produce a tube made from this material.

This solution might be out of the price range of the typical replicator.

Another idea is to use this glass as a surface coating just a few nanometers thick on both the inside and outside of a refractory metal tube using vapor disposition. Because we would be using a minimum of bulk material this method would not cost too much to do if the replicator can do it himself. The expansion of the coating would need to match the expansion coefficient of the refractory metal that is being used(tungsten?) .
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0 #61 EccoEcco 2015-10-05 04:32
@Robert Greenyer: hi and thanksthanks. I was unsure whether to use Ecco2 or not. As it would have been slightly awkward (ecCO2? ECco2?) and perhaps ecco-unfriendly , I opted for EccoEcco.
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0 #60 Robert Greenyer 2015-10-04 20:01
@EccoEcco

Welcome back Ecco, Love the new name! Better than EverEver!
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0 #59 EccoEcco 2015-10-03 14:16
If needed (since suitable ones, with no more than 1-2% wt. potassium content also seem hard to easily find - too much K apparently negatively affects ultra-dense hydrogen formation), iron oxide-potassium catalysts could be manually prepared from hematite, potassium carbonate and a "structural promoter" (needed to increase surface area and avoid sintering), such as chromium oxide or aluminium oxide. The mixed compound is calcined at a relatively high temperature (~600 °C), then partially reduced. This final partial reduction step is what makes the catalyst active. The process should be in some ways similar to Bob Higgins' sintered nickel-iron powder process as described here. Using Ni wouldn't be needed however:

on-the-rag.com/.../...

The processed powder could be compressed into pellets as some Russian researchers are doing with titanium powder. This would make handling easier. Lithium could still be used as a hydrogen getter somewhere in the reactor for inducing a continuous and more or less controlled hydrogen flux over the hydrogen splitting iron-potassium catalyst.


A related read:

researchgate.net/.../...

Quote:
The main precursors of the technical catalyst are hematite (Fe 2 O 3 ) and the promotor potassium carbonate (K 2 CO 3 ) which are mixed and calcined. Small amounts of other metal oxides like Cr 2 O 3 , are added as structural promoters to stabilize the catalyst morphology and prevent sintering. Promotion of iron oxide with potassium enhances the reactivity of iron oxide by an order of magnitude and reduces the formation of carbonaceous surface deposits (here shortly called coke) that deactivate the catalysts
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0 #58 axil 2015-10-01 20:41
I have been looking into alkali metal dispenser technology.

google.com/.../US20060257296

In some embodiments, an alkali metal dispenser composition of the present invention comprises:

a. an alkali metal source that comprises rubidium;
b. a getter for alkali metals that comprises gold;
c. a reducing agent that comprises carbon; and
d. an alloy, wherein the alloy comprises rubidium atoms from the alkali metal source (a) and gold atoms from the getter (b).

There are many chemical variations of this formulation current in the alkali metal dispenser business.

From the Lugano test report at the very end, the fuel mix that Rossi used included a number of elements in his fuel mix that were a puzzle. It is a puzzle that begs to be solved. Those elements might have been part of his lithium dispenser method. Rydberg matter may require that the alkili metal be ionized and reconvened as in vapor disposition. This may be why Rossi added those seemingly unrelated elements to his fuel mix. They may first combine with lithium at low temperatures, then re-emit the alkili metal in ionized form at higher temperatures from which Rydberg matter condenses.

It might be advantageous for the replicators of the Rossi reactor to look into how these alkali metal dispenser work. One concrete example of one is the iron oxide potassium catalyst that Holmlid uses in his experiments.

Also, the dirty and impure materials used by Parkhomov may be the key to why his reactors work and our clean replications do not.
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0 #57 Axil 2015-09-08 19:31
1 of 2

Reference:

citeseerx.ist.psu.edu/.../...

A novel model for the interpretation of the unidentified infrared (UIR)
bands from interstellar space: deexcitation of Rydberg Matter

I have been looking for ways to optimize production of Rydberg matter whose generation is discribed by Lief Holmlid in the reference above and except below.

We now report on a model in
which all UIR bands are due to electronic deexcitation in the
condensed phase named Rydberg Matter. This type of very low density
condensed matter is formed by condensation of Rydberg
states of almost any type of atom or small molecule, in space
mainly hydrogen atoms and molecules. The initial formation of
Rydberg states is due to desorption of alkali atoms from surfaces
of small particles, especially carbon particles. This desorption
can be caused by radiation or moderate heat and gives long lived
circular Rydberg states. Rydberg Matter can be produced
in macroscopic quantities in the laboratory.
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0 #56 Axil 2015-09-08 19:29
2 of 2

To meet this method of rydberg matter production using carbon based generation capability as suggested above, I looked for a chemical compound that would be superior to (LAH; Lithium tetrahydridoalu minate) that contained Carbon to enhance Rydberg matter production, an Alkali metal. and Hydrogen. I assumed that replacing aluminum with carbon would make a better catalyst for producing Rydberg matter. My search for a replacement led to two alkkali compounds in the same family as follows:

lithium hydrogen acetylide Li HC2
potassium hydrogen acetylide KHC2

See
en.wikipedia.org/.../Acetylide

When these acetylides are heated, hydrogen is released, then the alkali metel is released from the carbon as the temperature rises. After the release of hydrogen, potassium/lithi um carbide is formed. Potassium carbide was the active LENR material in the DGT reaction. In the old days, this stuff was used in miners lanterns to produce illuminating gas when water was added.

As a disclaimer, I am not a chemist, so I don’t know the toxicity and explosion risks of these compounds. Please help here.

IMHO, to test the Rydberg matter cause of LENR, a series of tests using one or both of these Acetylide based compounds might be worth a try.
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0 #55 Axil 2015-08-28 20:46
As documented in the AIRBUS patent, an alternative method in nanoparticle production is electric arcing. The arc produces the high temperatures and pressures needed for supersaturation in the gas that surrounds the arc. As seen in the experiment of Ken Shoulders, the arc will produce a zone of temperature and pressure drop at some distance from the arc where nanoparticles will form. The temperature and pressure drop that results when the arc stops will also meet the requirements of nanoparticle production. A rapidly repeating high voltage electric arc on/off cycle will maximize nanoparticle production in a gas mixture.
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+1 #54 Axil 2015-08-28 19:20
Part 4 of 4

The formation of nanoparticles are best supported in a supersaturated gas solution where the temperature and/or its pressure is constantly changing.

Heterogeneous nucleation of an alkali metal which includes hydrogen is supported by another alkali element metal(or chemical compound isoelectric mimics of the alkali metals) sitting on a transition metal substrate. The alkali deposits provides a template form which the nanoparticle will nucleate and grow. Examples of such nucleation template masks are potassium or lithium on the surface of iron or nickel. In the analysis of the Lugano fuel mix, lithium completely covered the 100 micron nickel fuel particle.

In theory, a mixture of potassium and lithium should support faster development at lower temperatures of a supersaturation condition of a hydrogen gas mixture than a mix using lithium only.
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+1 #53 Axil 2015-08-28 19:18
Part 3 of 4

The condition of supersaturation does not necessarily have to be reached through the manipulation of heat. The ideal gas law PV = nRT suggests that pressure and volume can also be changed to force a system into a supersaturated state. If the volume of solvent is decreased, the concentration of the solute can be above the saturation point and thus create a supersaturated solution. The decrease in volume is most commonly generated through evaporation. Similarly, an increase in pressure can drive a solution to a supersaturated state. All three of these mechanisms rely on the fact that the conditions of the solution can be changed quicker than the solute can precipitate or crystallize out.
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+1 #52 Axil 2015-08-28 19:17
Part 2 of 4

Special conditions need to be met in order to generate a supersaturated solution. One of the easiest ways to do this relies on the temperature dependence of solubility. As a general rule, the more heat is added to a system, the more soluble a substance becomes. (There are exceptions where the opposite is true). Therefore, at high temperatures, more solute can be dissolved than at room temperature. If this solution were to be suddenly cooled at a rate faster than the rate of precipitation, the solution will become supersaturated until the solute precipitates to the temperature-det ermined saturation point. The precipitation or crystallization of the solute takes longer than the actual cooling time because the molecules need to meet up and form the precipitate without being knocked apart by the solvent. Thus, the larger the molecule, the longer it will take to crystallize due to the principles of Brownian motion.
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+1 #51 Axil 2015-08-28 19:11
Part 1 of 2

Part 1 of 2

How does Rydberg Hydrogen Matter (RHM) form?

Nucleation is the first step in the formation of a new crystalline structure via self-assembly or self-organizati on. Nucleation is typically defined to be the process that determines how long an observer has to wait before the new phase or self-organized structure appears.

The probability that nucleation will begin is very sensitive to impurities present in the system. Because of this, it is often important to distinguish between heterogeneous nucleation and homogeneous nucleation. Heterogeneous nucleation occurs at nucleation sites on surfaces in the system. Homogenous nucleation occurs away from a surface. Rydberg matter formation begins with heterogeneous nucleation that occurs on a surface that hydrogen faces.

Nucleation is a stochastic process where random factors dominate. No two identical systems are identical so nucleation will occur at different times and at different rates.] This behavior is similar to radioactive decay. nucleation theory predicts that the time you have to wait for nucleation decreases extremely rapidly when supersaturated. Supersaturation implies that a solution of more than one element and/or compound and/or their associated phases are present in a mixture and the state of this solution contains more of the dissolved material than could be dissolved by the solvent under normal circumstances. It can also refer to a vapor of a compound that has a higher (partial) pressure than the vapor pressure of that compound.

For example, hydrogen and lithium can exist in a supersaturated mixture where hydrogen and/or lithium and/or lithium hydride can nucleate nanoparticles of hydrogen, lithium, and/or lithium hydride.
The generation of nanoparticles in a gas mixture is responsive to the manipulation of the supersaturating condition of the gas mixture.
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+1 #50 Robert Greenyer 2015-08-28 15:44
@Ecco

Yes I spotted that

Li is acting in several roles.
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+1 #49 Robert Greenyer 2015-08-28 14:25
look at this chart on wikipedia

en.wikipedia.org/.../...

the reactor is said to work from 250ºC - that means when the ionic Li + H- is first formed (LiH) - then if you take it to above 400ºC - the H is released and it forms LiAl which is a solid up to 702-720ºC apparently - having more Lithium will reduce this and leave LiAl in solution with molten Li. See this phase diagram

pruffle.mit.edu/.../img7.gif

Adding 30% Lithium lowers the melting point of the the combined metals to between 200ºC and 300ºC

2 LiH + 2 Al → 2 LiAl + H2

"Is reversible with an equilibrium pressure of about 0.25 bar at 500 °C"

see en.wikipedia.org/.../...

so this means you can make and destroy ionic Li+ H- (LiH) that will be in direct contact on or in porous Ni by varying temperature alone - you can make H- at will.
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+1 #48 Robert Greenyer 2015-08-28 11:28
New Fire Recipe?

GS3 *GlowStick* design reactor (AL2O3)

LaNi5H7 (HydroStik - do not charge with H2, take out powder) $20 see here for info goo.gl/eE3Pbz - goo.gl/XmwQxV (safe on planes)

LiAlH4 ( for Hydrogen release, need enough in sealed vessel to get to above 40 bar )

Free Lithium or better goo.gl/tmnECV

Bit of straight carbonyl Nickel for good measure

1. Heat core to below 179ºC - release 40+ bar of H2 from LiAlH4 - wait for LaNi5 to load
2. Raise temperature above melting point of Lithium quickly so it wets to Nickel before becoming LiH

temperature and proportions to be varied perhaps some selective RF

Now - Go bake a cake!
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