Atomic adsorption on graphene with a single vacancy: systematic DFT study through the periodic table of elements

Abstract

Vacancies in graphene present sites of altered chemical reactivity and open possibilities to tune graphene properties by defect engineering. The understanding of chemical reactivity of such defects is essential for successful implementation of carbon materials in advanced technologies. We report the results of a systematic DFT study of atomic adsorption on graphene with a single vacancy for the elements of rows 1-6 of the periodic table of elements (PTE), excluding lanthanides. The calculations have been performed using the PBE, long-range dispersion interaction-corrected PBE (PBE+D2 and PBE+D3) and non-local vdW-DF2 functionals. We find that most elements strongly bind to the vacancy, except for the elements of groups 11 and 12, and noble gases, for which the contribution of dispersion interaction to bonding is most significant. The strength of the interaction with the vacancy correlates with the cohesive energy of the elements in their stable phases: the higher the cohesive energy is, the stronger bonding to the vacancy can be expected. As most atoms can be trapped at the SV site we have calculated the potentials of dissolution and found that in most cases the metals adsorbed at the vacancy are more "noble" than they are in their corresponding stable phases.

Reactivity Screening of Single Atoms on Modified Graphene Surface: From Formation and Scaling Relations to Catalytic Activity

“…The adsorption energies and preferred binding sites on pristine and monovacant graphene are in good agreement with our previous studies of monoatomic adsorption on pristine and monovacant graphene [ 20,21 ] , as well as studies of various TM atoms adsorption on pristine graphene. [ 22,23 ] On pristine graphene, adsorption is preferential on the bridge and hollow sites, except for Au and Cu.…”

“…Point (i) can be quickly checked by comparing E ads (M) and cohesive energy of the corresponding metal ( E coh (M)), like in our previous work. [ 21 ] Briefly, if the adsorption energy of SA on a given support is negative and its absolute value is larger than the cohesive energy of the corresponding bulk metal phase, SA should be stable on the support. Such a comparison is presented in Figure .…”

“…This result agrees with a rule of thumb saying that higher cohesive energy of metal results with higher binding energy to the single vacancy site. [ 21 ]…”

Boosting Electrochemical Nitrogen Reduction Performance over Binuclear Mo Atoms on N-Doped Nanoporous Graphene: A Theoretical Investigation

“…To model the defective N-C monolayer, we first built a supercell containing 60 carbon atoms with a vacuum of at least 15 Å in the z-direction, and then removed six carbon atoms to provide an anchoring site for the single transition metal atom, or removed ten carbon atoms for the binuclear transition metal atoms. Based on the approach described in [38], formation energy was calculated, first, by the adsorption energy of metal atoms over N-doped graphene, and then further correlated with the experimentally obtained cohesive energy. Adsorption energy was calculated according to the equation: ∆E = E M-N-C − ( m E M + E NC ), where E M-N-C was the total energy of M-N-C sheet; E NC was the energy of the N-doped graphene without the metal atoms; E M was the energy of the isolated metal atom and m was the number of metal atoms in the system.…”

Modulation of Kekulé adatom ordering due to strain in graphene

“…Intervalley scattering may be important at the edges of a generic graphene flake [10,11], at substitutional dopants [12][13][14], and at certain adatoms [15] that adsorb to graphene in a "top" configuration (i.e., adsorbed atop individual carbon atoms), such as fluor [16] and hydrogen [17], thereby breaking sublattice symmetry. Despite destroying the chiral nature of carriers in graphene, intervalley scattering is also fundamentally interesting in its own right [18] and can actually become a powerful tool, particularly for graphene functionalization.…”