Rapid, low-temperature nanodiamond formation by electron-beam activation of adamantane C–H bonds

Diamond and adamantane (<b>Ad</b>) share a <i>T</i>_d-symmetric carbon skeleton, but converting <b>Ad</b> to diamond has been challenging because it requires selective carbon-hydrogen (C-H) bond cleavage and monomer assembly into a diamond lattice. Our approach differs from the conventional high-temperature, high-pressure diamond syntheses. We electron-irradiated <b>Ad</b> submicrocrystals at 80 to 200 kilo-electron volts and 100 to 296 kelvin in vacuum for tens of seconds. This process yielded defect-free nanodiamonds (NDs) of cubic crystal structure, accompanied by hydrogen gas evolution. Time-resolved transmission electron microscopy revealed the initial formation of <b>Ad</b> oligomers transforming into spherical NDs. A sizable kinetic isotope effect indicates that C-H cleavage was rate-determining, and other hydrocarbons tested failed to form NDs.