Nanodiamond
synthesized by the detonation method is a composite of sp3/sp2 carbon structures; amorphous and disordered-sp2 carbons populate the surface of a sp3 diamond
core lattice. Because of the production process, various elemental
impurities such as N, O, H, and so forth are inherent in interstitial
sites or the surface carbon (sp2/amorphous) network. Herein,
the reaction dynamics on the surface of ultradisperse diamond (UDD)
due to the surface transformation or reconstruction during annealing
in vacuum with temperatures ranging from ambient to 800 °C is
described. In situ measurement of Fourier transform infrared spectroscopic
analysis shows that low-temperature (<500 °C) annealing of
UDD in vacuum results in isonitrile/isocyanide (−N=C:)
and nitrile functionalization (−C≡N) on the surface.
At temperatures ∼500 °C, the surface hydrogenation of
UDD is initiated. During annealing at 780–800 °C, the
nitrile group (−C≡N) is reduced to the primary amine
(NH2), and isonitrile (−N=C:) turns it to
be in the saturated ()
structure. On exposure to air, the obtained isonitrile is transformed
to an N-formyl derivative (Aryl/R–NH–CHO)
structure via hydrolysis. This study provides a fundamental insight
into the surface reactive profile of UDD which could lead to facile
surface functionalization properties and their applications in various
fields such as biomedical, biosensing, drug delivery, epoxy materials
process, tribology, and possibly in cyano (−C≡N/–N=C:)
chemistry.