Nobel Laureate George Olah, carbon dioxide fixation, and fuel cells.

[NNadir]

Frequently I find myself in insipid debates with mindless twits who at some point engage in the logical fallacy of "Appeal to Authority" to support stupid positions.

(I certainly hope I didn't mince words in that sentence.)

Most often arguments involving Appeal to Authority are notable for the appeal to people who are highly regarded in one area, but not competent in another. A famous example would be William Shockley, who one the Nobel Prize in Physics and then used is Nobel stature to advance racist genetic theories. Because of his stature in physics, he was able to garner some attention to his racist theories even though he clearly knew less about genetics than most people. For some people it was probably enough simply to claim that he was a "smart guy." Probably, in fact, he was nearly illiterate on the subject of genetics, even more than most, since he saw the entire subject through the prism of profound bias.

As I was thinking about the subject of this most annoying logical fallacy however, to which I am often subject to my complete disgust, I realized that sometimes the fallacy is applied by appeal people who either are competent in an area or should be assumed to be competent in that area but are nonetheless wrong anyway. This is because even people who are highly skilled and highly knowledgeable can still make mistakes and draw inappropriate conclusions. In other words, sometimes even the best make mistakes.

This line of thinking lead me to reflect on the great chemist Herbert C. Brown, who shared a Nobel prize with George Wittig for their work, respectively on organoborane and organophosphorous chemistry. After his prize winning work, Dr. Brown sank himself into the matter of the nonclassical norborenyl carbocation proposed by Saul Winstein. Brown expended great energy arguing that such an ion did not exist, and that the results of experiments that seemed to suggest it were better explained by the existence of two discrete, but rapidly interchanging ions. It’s been some years since I contemplated this matter, but I recall, in the days before “on line” searching, before the internet, reading some of the heated papers on the subject. I always remember thinking that Brown’s papers on the subject deserved special status because he was, after all, a Nobel Laureate. Though it seemed that he was wrong well, he couldn’t be. Because of his Nobel he was in the pantheon of the great chemists.

In spite of his Nobel stature, however it turns out that Dr. Brown was wrong. The non-classical ion does indeed exist and has been unambiguously been identified in “magic ion” NMR experiments and in many other ways. The ion is indeed non-classical: The positive charge associated with the cation is not located on a single carbon but is actually distributed over several carbons.

Because the internet makes searching so easy, my reflection on the subject of logical fallacy led me, as an aside, to look into the question of the cation again, since it is easy to do and no longer involves a trip to the library. As a result, I stumbled upon this article, http://pubs.acs.org/cen/coverstory/83/8311georgeolah1.html
the brief autobiography of George Olah. Dr Olah, who would himself win a Nobel for his work on carbocations, relates how as a young chemist, he was challenged by the two great antagonists in the carbocation world, Winstein and Brown:

“Stable (persistent) carbocation studies involved not only the usual trivalent but also five- and higher-coordination ions. The much-publicized, so-called nonclassical ion controversy centered mainly on the case of the norbornyl cation. The 1962 Brookhaven Mechanism Conference, where I first reported on our work on long lived carbocations in public, is still clear in my mind. The scheduled “main event” of the meeting was the continuing debate between Saul Winstein and Herbert Brown on the classical or nonclassical nature of the norbornyl cation. It must have come as a surprise to them and to the audience that a young chemist from an industrial laboratory had been invited to lecture on having obtained and studied stable, longlived carbonium ions (as they were still called at the time) by the new method of using highly acidic (superacidic) systems.

I remember being called aside separately during the conference by Winstein and by Brown, both towering and dominating personalities of the time, who cautioned me that a young man should be exceedingly careful in making such claims. Each pointed out that most probably I was wrong and could not have obtained long-lived carbonium ions. Just in case my method turned out to be real, however, I was advised to obtain evidence for the “nonclassical” or “classical” nature (depending on who was giving the advice) of the much-disputed 2-norbornyl cation. Eventually, the norbornyl ion turned out to be the ó-delocalized higher coordinate nonclassical ion and not a pair of equilibrating trivalent classical ions. This ended the dispute and a much-discussed chapter of physical-organic chemistry.”

All of this has a point relevant to this forum, which is that George Olah’s most recent work is very much involved in the question of chemical strategies for the mitigation of global climate change. To this end, Dr. Olah has been working in recent years on the question of the reduction of carbon dioxide to liquid fuels, in his case methanol. Indeed, Olah has worked extensively on the topic of the direct use of methanol in fuel cells. He writes:

“…our research continues to center on the study of new hydrocarbon chemistry. We search for new approaches to produce and utilize hydrocarbons beyond the availability of nonrenewable and relatively cheap oil and gas.

The major effort of our present research is directed toward developing an approach that I call the “methanol economy.” The approach involves producing methanol directly from still-abundant vast natural gas resources (that is, methane) without going through syngas. More important, we also pursue new chemistry to reductively convert carbon dioxide to methanol. CARBON DIOXIDE can be readily separated from flue gases of coal-burning power plants or industrial plants. Rather than just sequestering CO2, the gas can be used for producing methanol-based fuels and raw materials for hydrocarbons. I believe that, using selective absorption methods and membrane technology, it will be eventually even feasible to separate atmospheric CO2 itself (representing only 0.036% of air) and convert it into methanol, thus freeing humankind of its reliance on diminishing fossil fuels. Of course, to produce the needed hydrogen by electrolysis of water, much energy is needed, which will be provided by atomic energy and the use of all alternative energy sources. Other approaches (photocatalytic, enzymatic, etcetera) also offer possibilities.

Methanol, a convenient liquid, is a way to store and transport energy. Methanol is also an excellent fuel in its own right, including its use in the direct methanol fuel cell (DMFC) that we developed jointly with the Jet Propulsion Laboratory of California Institute of Technology. Methanol, significantly, can also be directly converted catalytically into ethylene or propylene and subsequently to varied hydrocarbons and their products presently obtained from oil and natural gas. Once it becomes economically feasible to chemically recycle atmospheric CO2, the process will also supplement nature’s photosynthesis to mitigate the effect of this major greenhouse gas on global warming. We are involved in extensive research on all these issues…”

I often write that there isn’t really that much time left to solve the global climate change crisis, in my opinion. It is my opinion that we must adopt the best means immediately available and cannot assume success for promising research. That said, I find Dr. Olah’s work exciting and I hope that such time remains for us as to be able to apply it. Although I am not particularly sanguine about methanol (owing to its toxicity) Dr. Olah does point out that a safer world is at least theoretically possible.

Of course, as usual, I cannot refrain from pointing out that Dr. Olah represents yet another high level scientist who recognizes and clearly states the need to go nuclear.