Chemically induced graphene to diamond transition: a DFT study

The conversion of graphene into diamond is a new way for preparing ultrathin diamond film without pressure. Herein, we investigated the transformation mechanism of surface-hydrogenated bilayer graphene (SHBG) into surface-hydrogenated single-layer diamond (SHSLD) crystal, inserting fifteen kinds of single metal atoms without any pressure, by using the systematical first-principles calculations. Compared with the configuration without metal atom, SHBG can be transformed into SHSLD spontaneously in thermodynamics under the action of single metal atom, and its formation energy can even decrease from 0.82 eV to -5.79 eV under the action of Hf atom. According to our results, the outer electron orbits and atomic radius of metal atom are two important factors that affect the conversion. For the phase transition to occur, the metal atom needs to have enough empty d orbitals, and the radius of the metal atom is in the range of 0.136-0.159 nm. Through further analysis, we find that the p orbitals of carbon atoms and d orbital of metal atom in SHBG will be strongly hybridized, thereby promoting the conversion. The results supply important significance to experimentally prepare diamond without pressure through hydrogenated graphene.