"Poisoning" Ni reactive sites-- replicators note

Quoting Dr. Peter Gluck, now one of the grandfathers of LENR, concerning a very important parameter that may be missed by replicators (in Longview's opinion, at least):

"I have learned from professor Francesco Piantelli the essential importance of deep degassing- before putting nickel in contact with hydrogen, the surface of the metal must be absolutely free of any molecules of gas. This is so well described in EP2368252 "

[end quote, from a link at Peter's Blogspot Ego Out, that link citing Yiannis Hadjichristos is here: http://egooutpeters.blogspot.r…lenr-will-never-work.html.]

I am impressed by the early and definitive acceptance of the notion of catalysis as a key parameter in determining successful LENR / CANR / CF by Peter Gluck and others. To me, this is really a key central feature, and here Peter and others are offering a very good reason for the unpredictable behavior of CF experiments. I am sure there are other variables. One only has to look at the history of semiconductors and the long path to ultimately understand that ultrapurification of germanium and silicon (ultimately by zone refining) was a necessary step toward consistent operation of semiconductor electronics and ultimately to the transistor in 1948.

In chemical process engineering, catalyst poisoning is an undisputed fact. It can make a good catalyst non-functional. Essentially the addition of a single molecule of poison (Peter suggests nitrogen, the major constituent of air) in each of the active sites can kill a catalyst forever more. Analogously in biology, "receptors" and "active sites" show us that Inhibitory binding to such sites is very often much stronger than "active" binding.

Such "poisoning" may be an important point for replicators to attend to. With the caveat that greatly enhancing the efficiency of LENR by such attention might easily result in a destructive level of energy production. Small is beautiful in this case. A small blowup is always "nicer" than a big one.

Quote from FreethinkerLenr2

Quoting from the patent from Peter Gluck's Comment:
"bringing hydrogen into contact with said clusters and controlling its pressure and speed, preferably after applying vacuum cycles of at least 10-9 bar between 350° and 500°C for degassing the clusters"

Out of curiosity and because you seem well rooted in the trade, what would degas 1-50 micron particles, in particular? Would you have a reference? I am asking, since the 10^-9 bar is a tall order to uphold, and at those temperatures, especially if we talk off the shelf stuff for diy guys.

I am only modestly experience with vacuum degassing. But I believe this is not exceedingly difficult. The pressure advocated there is low but not quite ultra low. that is it is above 10^-7 torr. Further, the use of some other purge gas that will not react with or strongly bind the nickel sites will greatly accelerate clearing the atmospheric gases (perhaps helium--- if that does not cause other problems). Also, a higher range of temperature will help, that is no less than 500 C---. The main thing is to drive nitrogen off the active sites, such as they may be. One should be able to get to very low residual nitrogen and oxygen levels in this way, far lower than the usual high vacuum with modest heat alone. Ion beam etching of the surfaces may be another related option.

Quote from ogfusionist

Sulfur is the most active poisoning element. Hydrogen firing is the most effective means of removing sulfur by formation of hydrogen sulfide and sweeping away with hydrogen flow.

"since the 10^-9 bar is a tall order to uphold, and at those temperatures, especially if we talk off the shelf stuff for diy guys."

We're not talking 10^-9 bar, we're talking partial pressures of less than 10^-10 torr to effectively remove sulfides from the catalyst surface.

But is that true for the CF / LENR catalytic function? It would not surprise me, since nickel subsulfide or whatever nickel sulfide, surely differs chemically from nickel itself.

I recall that once you wrote that your process for LENR involved a vacuum bake out. But a hydrogen bake out sounds like after the sulfides were removed--- and that led to your thermal runaway.... yes?

Before giving up to very high vacuum bake outs and so on. I would look at silver or copper, which both react more vigorously with sulfur than does hydrogen. Just a speculation at this point, but citric acid (or potassium citrate) and silver nitrate solution should give a soluble silver sulfide that can be washed away. That rinse can be regenerated to save the silver.

Another approach: nickel sulfide is soluble in nitric acid. It may be possible to expose sulfur contaminated nickel to nitric acid, rinse off the nickel sulfide-- nitrate adduct.

Another possibility is to use a solution of nickel nitrate, which itself is acidic and oxidizing, while being unlikely to corrode pure nickel itself, since it is ionically in equilibrium with nickel.

Also, of some note, is that our old friend nickelous oxide on fibrous alumina for your "LENR" --- NiO is mentioned as route to nickel (II) nitrate via NiO + HNO3.

Another: nickel nitrate itself is often used as a precursor for developing nickel on supported catalysts.

Quote from ogfusionist

Without control of catalyst poisoning attempting replication is useless. Because of the prevalance of sulfur in our atmosphere the hydrogen used for the fusion reaction must be pre purified. I used silver to drop the H2S concentration below the detection limit of the RGA (10^-10 torr).

We're now getting to the heart of problems with replication. Sulfur displaces oxygen on the atomic surface layer of the catalyst and at operating temperature is permanently bound. It's important after applying the high purity NiO that H2S never reaches the surface.

It seems plausible to allow the hydrogen itself to clean the nickel or NiO of sulfur / sulfides. At high enough temperatures an ultrapure "electronic" grade of hydrogen will form hydrogen sulfide in an energetically favorable reaction, essentially extracting resident sulfur from the nickel. Once that highly volatile H2S gas is formed it can migrate or be pumped to a copper "getter" elsewhere in the reactor cell-- or even as an inline filter in a hydrogen recirculator, since it is likely there is a lower ideal temperature for favoring irreversible binding of copper to sulfur. The copper getter can be periodically replaced and/or stripped of accumulated sulfide--- many practical configuratons are possible, depending on specific chemistries.