Gaseous Nanocarving-Mediated Carbon Framework with Spontaneous Metal Assembly for Structure-Tunable Metal/Carbon Nanofibers.

Vapor phase carbon (C)-reduction-based syntheses of C nanotubes and graphene, which are highly functional solid C nanomaterials, have received extensive attention in the field of materials science. This study suggests a revolutionary method for precisely controlling the C structures by oxidizing solid C nanomaterials into gaseous products in the opposite manner of the conventional approach. This gaseous nanocarving enables the modulation of inherent metal assembly in metal/C hybrid nanomaterials because of the promoted C oxidation at the metal/C interface, which produces inner pores inside C nanomaterials. This phenomenon is revealed by investigating the aspects of structure formation with selective C oxidation in the metal/C nanofibers, and density functional theory calculation. Interestingly, the tendency of C oxidation and calculated oxygen binding energy at the metal surface plane is coincident with the order Co > Ni > Cu > Pt. The customizable control of the structural factors of metal/C nanomaterials through thermodynamic-calculation-derived processing parameters is reported for the first time in this work. This approach can open a new class of gas-solid reaction-based synthetic routes that dramatically broaden the structure-design range of metal/C hybrid nanomaterials. It represents an advancement toward overcoming the limitations of intrinsic activities in various applications.