Tag Archives: H2S

Low temperature hydrogen removal

Platinum catalysts can be very effective at removing hydrogen from air. Platinum promotes the irreversible reaction of hydrogen with oxygen to make water: H2 + 1/2 O2 –> H2O, a reaction that can take off, at great rates, even at temperatures well below freezing. In the 1800s, when platinum was cheap, platinum powder was used to light town-gas, gas street lamps. In those days, street lamps were not fueled by methane, ‘natural gas’, but by ‘town gas’, a mix of hydrogen and carbon monoxide and many impurities like H2S. It was made by reacting coal and steam in a gas plant, and it is a testament to the catalytic power of Pt that it could light this town gas. These impurities are catalytic poisons. When exposed to any catalyst, including platinum, the catalyst looses it’s power to. This is especially true at low temperatures where product water condenses, and this too poisons the catalytic surface.

Nowadays, platinum is expensive and platinum catalysts are no longer made of Pt powder, but rather by coating a thin layer of Pt metal on a high surface area substrate like alumina, ceria, or activated carbon. At higher temperatures, this distribution of Pt improves the reaction rate per gram Pt. Unfortunately, at low temperatures, the substrate seems to be part of the poisoning problem. I think I’ve found a partial way around it though.

My company, REB Research, sells Pt catalysts for hydrogen removal use down to about 0°C, 32°F. For those needing lower temperature hydrogen removal, we offer a palladium-hydrocarbon getter that continues to work down to -30°C and works both in air and in the absence of air. It’s pretty good, but poisons more readily than Pt does when exposed to H2S. For years, I had wanted to develop a version of the platinum catalyst that works well down to -30°C or so, and ideally that worked both in air and without air. I got to do some of this development work during the COVID downtime year.

My current approach is to add a small amount of teflon and other hydrophobic materials. My theory is that normal Pt catalysts form water so readily that the water coats the catalytic surface and substrate pores, choking the catalyst from contact with oxygen or hydrogen. My thought of why our Pd-organic works better than Pt is that it’s part because Pd is a slower water former, and in part because the organic compounds prevent water condensation. If so, teflon + Pt should be more active than uncoated Pt catalyst. And it is so.

Think of this in terms of the  Van der Waals equation of state:{\displaystyle \left(p+{\frac {a}{V_{m}^{2}}}\right)\left(V_{m}-b\right)=RT}

where V_{m} is molar volume. The substance-specific constants a and b can be understood as an attraction force between molecules and a molecular volume respectively. Alternately, they can be calculated from the critical temperature and pressure as

{\displaystyle a={\frac {27(RT_{c})^{2}}{64p_{c}}}}{\displaystyle b={\frac {RT_{c}}{8p_{c}}}.}

Now, I’m going to assume that the effect of a hydrophobic surface near the Pt is to reduce the effective value of a. This is to say that water molecules still attract as before, but there are fewer water molecules around. I’ll assume that b remains the same. Thus the ratio of Tc and Pc remains the same but the values drop by a factor of related to the decrease in water density. If we imagine the use of enough teflon to decrease he number of water molecules by 60%, that would be enough to reduce the critical temperature by 60%. That is, from 647 K (374 °C) to 359 K, or -14°C. This might be enough to allow Pt catalysts to be used for H2 removal from the gas within a nuclear wast casket. I’m into nuclear, both because of its clean power density and its space density. As for nuclear waste, you need these caskets.

I’ve begun to test of my theory by making hydrogen removal catalyst that use both platinum and palladium along with unsaturated hydrocarbons. I find it works far better than the palladium-hydrocarbon getter, at least at room temperature. I find it works well even when the catalyst is completely soaked in water, but the real experiments are yet to come — how does this work in the cold. Originally I planned to use a freezer for these tests, but I now have a better method: wait for winter and use God’s giant freezer.

Robert E. Buxbaum October 20, 2021. I did a fuller treatment of the thermo above, a few weeks back.

Highest temperature superconductor so far: H2S

The new champion of high-temperature superconductivity is a fairly common gas, hydrogen sulphide, H2S. By compressing it to 150 GPa, 1.5 million atm., a team lead by Alexander Drozdov and M. Eremets of the Max Planck Institute coaxed superconductivity from H2S at temperatures as high as 203.5°K (-70°C). This is, by far, the warmest temperature of any superconductor discovered to-date, and it’s main significance is to open the door for finding superconductivity in other, related hydrogen compounds — ideally at warmer temperatures and/or less-difficult pressures. Among the interesting compounds that will certainly get more attention: PH3, BH3, Methyl mercaptan, and even water, either alone or in combination with H2S.

Relationship between H2S pressure and critical temperature for superconductivity.

Relation between pressure and critical temperature for superconductivity, Tc, in H2S (filled squares) and D2S (open red). The magenta point was measured by magnetic susceptibility (Nature)

H2S superconductivity appears to follow the standard, Bardeen–Cooper–Schrieffer theory (B-C-S). According to this theory superconductivity derives from the formation of pairs of opposite-spinning electrons (Cooper pairs) particularly in light, stiff, semiconductor materials. The light, positively charged lattice quickly moves inward to follow the motion of the electrons, see figure below. This synchronicity of motion is posited to create an effective bond between the electrons, enough to counter the natural repulsion, and allows the the pairs to condense to a low-energy quantum state where they behave as if they were very large and very spread out. In this large, spread out state, they slide through the lattice without interacting with the atoms or the few local vibrations and unpaired electrons found at low temperatures. From this theory, we would expect to find the highest temperature superconductivity in the lightest lattice, materials like ice, boron hydride, magnesium hydride, or H2S, and we expect to find higher temperature behavior in the hydrogen version, H2O, or H2S than in the heavier, deuterium analogs, D2O or D2S. Experiments with H2S and D2S (shown at right) confirm this expectation suggesting that H2S superconductivity is of the B-C-S type. Sorry to say, water has not shown any comparable superconductivity in experiments to date.

We have found high temperature superconductivity in few of materials that we would expect from B-C-S theory, and yet-higher temperature is seen in many unexpected materials. While hydride materials generally do become superconducting, they mostly do so only at low temperatures. The highest temperature semiconductor B-C-S semiconductor discovered until now was magnesium boride, Tc = 27 K. More bothersome, the most-used superconductor, Nb-Sn, and the world record holder until now, copper-oxide ceramics, Tc = 133 K at ambient pressure; 164 K at 35 GPa (350,000 atm) were not B-C-S. There is no version of B-C-S theory to explain why these materials behave as well as they do, or why pressure effects Tc in them. Pressure effects Tc in B-C-S materials by raising the energy of small-scale vibrations that would be necessary to break the pairs. Why should pressure effect copper ceramics? No one knows.

The standard theory of superconductivity relies on Cooper pairs of electrons held together by lattice elasticity.  The lighter and stiffer the lattice, the higher temperature the superconductivity.

The standard theory of superconductivity relies on Cooper pairs of electrons held together by lattice elasticity. The lighter and stiffer the lattice, the higher temperature the superconductivity.

The assumption is that high-pressure H2S acts as a sort of metallic hydrogen. From B-C-S theory, metallic hydrogen was predicted to be a room-temperature superconductor because the material would likely to be a semi-metal, and thus a semiconductor at all temperatures. Hydrogen’s low atomic weight would mean that there would be no significant localized vibrations even at room temperature, suggesting room temperature superconductivity. Sorry to say, we have yet to reach the astronomical pressures necessary to make metallic hydrogen, so we don’t know if this prediction is true. But now it seems H2S behaves nearly the same without requiring the extremely high pressures. It is thought that high temperature H2S superconductivity occurs because H2S somewhat decomposes to H3S and S, and that the H3S provides a metallic-hydrogen-like operative lattice. The sulfur, it’s thought, just goes along for the ride. If this is the explanation, we might hope to find the same behaviors in water or phosphine, PH3, perhaps when mixed with H2S.

One last issue, I guess, is what is this high temperature superconductivity good for. As far as H2S superconductivity goes, the simple answer is that it’s probably good for nothing. The pressures are too high. In general though, high temperature superconductors like NbSn are important. They have been valuable for making high strength magnets, and for prosaic applications like long distance power transmission. The big magnets are used for submarine hunting, nuclear fusion, and (potentially) for levitation trains. See my essay on Fusion here, it’s what I did my PhD on — in chemical engineering, and levitation trains, potentially, will revolutionize transport.

Robert Buxbaum, December 24, 2015. My company, REB Research, does a lot with hydrogen. Not that we make superconductors, but we make hydrogen generators and purifiers, and I try to keep up with the relevant hydrogen research.