Functionalized diamond nanothreads from benzene derivatives

Abstract

Diamond nanothreads (DNTs) are fully sp-bonded one-dimensional carbon nanostructures, synthesized recently through compression of crystalline benzene. They possess outstanding mechanical strength, suitable for the development of novel nanostructured reinforced materials. In this article, we use density functional theory calculations to investigate the feasibility and physical properties of functionalized DNTs. We show that the stacking and covalent bonding of benzene derivative molecules (toluene, aniline, phenol and fluorobenzene) may lead to stable configurations analogous to benzene-derived DNTs, with functional groups (-CH, -NH, -OH, -F) covalently attached to the surface. The same principle was also applied to pyridine, an aromatic heterocyclic compound, resulting in DNTs containing N heteroatoms within the sp C-C chain. We show that the mechanical properties remain practically unaltered compared to the original material, and that the electronic properties can be tuned upon functionalization. The presence of polar functional groups on DNT surfaces are expected to affect their compatibility with other materials and solvents, enabling the development of novel processes and technological applications using DNTs.

One-dimensional diamondoid polyaniline-like nanothreads from compressed crystal aniline

“…The properties of different functionalized diamond nanothreads have been recently computed by DFT calculations. 33 These materials correspond to the possible products of high-pressure transformations of both functionalized benzene and heteroaromatic rings. Interestingly, the functionalized diamond nanothreads maintain the mechanical properties of the pristine material but offer, depending on the functional group and its spatial distribution, the possibility of tuning the band gap.…”

“…According to these predictions the NH 2 -enriched carbon polyaniline-like nanothread is expected to present a band gap in the order of 3.5 eV, an essentially insulating material due to the intrinsic carbon sp 3 character, an ideal strength of ∼14.8 nN, a Young’s modulus of 163 nN and a fracture strain ( ε max ) of ∼0.16. 33 Moreover, the synergic effect between these remarkable mechanical properties with the versatility of the NH 2 groups decorating the exterior of these nanothreads representing potential active sites for doping and as linkers for molecules with biological interest and inorganic nanostructures, must be taken into account.…”

High density mechanical energy storage with carbon nanothread bundle

“…Experiments have already demonstrated the feasibility of functionalizing nanothreads with -NH 2 groups 23 , which decorate the exterior of the nanothreads and acts as potential linkers for adjacent nanothreads. DFT calculations 43 show the possibility of functionalizing with various functional groups (e.g. -CH 3 , -NH 2 -OH, and -F), while retaining the mechanical properties of nanothreads.…”

Synthesis of double core chromophore-functionalized nanothreads by compressing azobenzene in a diamond anvil cell

“…Ab initio DFT calculations and classical MD simulations suggested the formation of fully saturated carbon nanothreads from polycyclic aromatic hydrocarbons 21 and from substituted benzenes (-CH 3 , -NH 2 , -OH, and -F). 22 The presence of such groups is extremely attracting in view of exploiting them for functionalization or for tuning the electronic properties without reducing the mechanical properties which are not substantially altered upon functionalization with respect to benzene derived nanothreads. The presence of unsaturation can also play an important role in tuning the electronic properties by changing the gap from the UV to the near infrared, but obviously decreasing both strength and stiffness with respect to fully saturated nanothreads.…”