The IUPAC compendium of technology states: "previously, descriptions such as graphite layers, carbon layers, or carbon sheets have been used for the term graphene… it is incorrect to use for a single layer a term which includes the term graphite, which would imply a three-dimensional structure. The term graphene should be used only when the reactions, structural relations or other properties of individual layers are discussed."
Was the super material graphene discovered in the 20th century by chemist Hanns-Peter Boehm in Germany 1961, written about and then forgotten, or discovered in the 21st century by Russian physicists Andre Geim and Kostya Novoselov working at Manchester University, England in 2004? At stake are the bragging rights between Britain and Germany and the bragging rights between chemists and physicists, but little else.
Like most great new discoveries, once the public discovery is made (2004,) it is often possible to trawl back through previous publications to see earlier near misses, and sometime unrecognised hits. This seems to be the case with graphene, although the definition of graphene seems to have altered slightly over the years. To German chemists, Herr Boehm should get the credit, even if his publication didn’t spur scientific excitement and went on to be forgotten. His work also seems to have had earlier near misses. To the Brits, who naturalised the two Russian physicists, and who used different methodology which excited the scientific community on publication, it’s the 2004 discovery that matters, not the earlier near miss back in 1961. It was certainly the 2004 publication that generated all the current interest and research.
Below, the alternative view of the missed opportunity of 1961. Follow the link for some lively discussion in the comments section for whether Herr Boehm made an unrecognised hit or a mere near miss. Either way, I wonder where we would be now, if graphene had been properly recognised in 1961.
Boehm’s 1961 isolation of graphene
Physicists studying graphene may not be familiar with his work, but Hanns-Peter Boehm is well known among chemists. He and coauthors isolated and identified single graphene sheets by transmission electron microscopy (TEM) and X-ray diffraction in 1961 and authored the IUPAC (International Union of Pure and Applied Chemistry) report formally defining the term graphene in 1994. He must have been surprised to learn of its discovery in 2004. »
With coworkers Clauss, Fischer, and Hofmann, Boehm took an approach that continues to receive attention today, obtaining graphene via intermediate conversion to graphene oxide. It had long been known that bulk graphite could be oxidized by exposure to a potassium (or potassium permanganate)/sulfuric acid solution. The resulting graphite oxide (GO) interlayer spacing is expanded by a factor of two or three in comparison to graphite, and is susceptible to further expansion by introduction of polar liquids, as detailed in the 1962 paper:
The fact that the properties of graphene had not yet been measured and that it was thought not to be stable in its free form intrigued Andre Geim so much that in late 2002 he asked a new PhD student to see how thin he make a piece of graphite by polishing it down. This did not lead to sufficiently thin slices of material, but developed into one of Andre’s “Friday evening experiments” for Kostya Novoselov who was working on another project at the time. The term “Friday evening experiment” was used to describe a set of off beat, interest driven experiments but cunningly disguised the actual amount of work required to get any results. Having discussed the problem with friends and colleagues it was suggested by Oleg Shklyarevskii, a senior fellow from Kharkov, Ukraine that the material he threw away on the tape that was used to peel graphite and expose a clean surface for studies in surface science was thinner than the material Andre’s student had produced by polishing.