First‐Principles Study of Metal Atoms Adsorption on 2D Dumbbell C₄N

Abstract

Similar to graphene, zero bandgap is found in the recently proposed 2D dumbbell C4N (DB C4N), which limits its applications as electronic devices. Surface adsorption effectively modifies the electronic and magnetic properties of the 2D materials. Herein, the adsorption behaviors of 16 metal atoms adsorbed on the DB C4N, including alkali metals, alkaline earth metals, 3d transition metals (TMs), and precious metals, are investigated using the density functional theory. The electronic and magnetic properties of the adatom–C4N systems are systematically explored by analyzing the adsorption energies, the density of states (DOS), the band structures, the charge transfer, the total magnetic moments, the work function, and the dipole moment. It is revealed that the alkali metals (Li, Na), alkaline‐earth metals (Be, Mg), 3d TMs (Ti, V, Cr, Mn, Fe, Co), and precious metals (Ag, Pt, Au) open the zero bandgap of DB C4N via charge transfer between the adatoms and the DB C4N surface. Moreover, the 3d transition and precious metals adatoms induce magnetism in the monolayer C4N. These results qualify the metal‐adsorbed C4N systems as promising candidates for building outstanding electronic and spintronic devices in the future.

DFT-Guided Design and Fabrication of Carbon-Nitride-Based Materials for Energy Storage Devices: A Review

“…Reproduced with permission from Ref. [ 30 ]. l Top (upper) and side (lower) view of the atomic structure of C 5 N monolayer.…”

“…Bhuriyal et al also reported the first-principle study of C 3 N monolayer as a promising anode material for SIBs and PIBs, and they showed that multilayer adsorption of the metal atoms generated a high capacity of 1072 mAh g −1 and low diffusion barrier of 0.03 and 0.07 eV for Na and K-ion [ 55 ]. Xu et al showed that metal ion (Li, Na, and K) adsorption on C 4 N is an effective way to open the zero bandgap and modulate the electronic property because the adsorbed metal ion transfers charges to the surface of DB C 4 N [ 30 ].…”

Adsorption Mechanisms of Alkali Metal, Alkaline Earth Metal, and Halogen Atoms on Van der Waals Materials

“…The calculations were performed using the Vienna Ab initio Simulation Package (VASP), − with the projector-augmented wave (PAW) method , considering the spin polarization. The Perdew–Burke–Ernzerhof (PBE) functional including van der Waals corrections (PBE-TS) was employed, as this functional has been used to calculate the charge transfer between adatoms and vdW materials. ,,,, The plane-wave cutoff energy was set to 550 eV. The Brillouin zones of the unit cell of the bulk vdW materials were sampled with a 15 × 15 × 7 Γ-centered Monkhorst-Pack k -point mesh .…”

“…The Perdew−Burke−Ernzerhof (PBE) 43 functional including van der Waals corrections (PBE-TS) 44 was employed, as this functional has been used to calculate the charge transfer between adatoms and vdW materials. 25,26,30,37,45 The plane-wave cutoff energy was set to 550 eV. The Brillouin zones of the unit cell of the bulk vdW materials were sampled with a 15 × 15 × 7 Γ-centered Monkhorst-Pack k-point mesh.…”

“…According to the theoretical models of the surface adsorption on metallic surfaces, the density-of-states (DOS) of an adsorbate broadens from a delta function at infinite separation to a Lorentz-type distribution at the proximity of the surface. − While the width of the level is determined by the magnitude of the hopping integral of the surface–adsorbate system, the shift of the peak is caused by various factors including the image potential, the level mixing, and the surface barrier . These models were also applied to surface adsorption on graphene, − and the results showed that the magnitude of the charge transfer between different adatoms and the same substrate decreases monotonically from top to bottom through the alkali metal atoms or halogen atoms along with the periodic table. , Using the first-principles simulations, however, researchers frequently found that the charge transfer between adatoms and graphene does not vary monotonically with the electronegativity of the adatoms, and the sodium atom was difficult to be adsorbed on a graphene surface. − Furthermore, the Li atom was found to be adsorbed on the freestanding h-BN sheet weakly whereas on the 1T-MoS 2 monolayer strongly, and Zhu et al used 1T-MoS 2 as a high rate anode for sodium-ion batteries, which had a high capacity. − In addition, the calculations of adatoms on silicene, MoS 2 , stanene, SiC, and C 4 N − suggested that not only the electronic structure but also the surface structure affects the surface binding. These results indicate that the binding between adatoms and substrates is determined by the properties of both the adatoms and the vdW substrates, the detailed mechanism of which is far from being fully understood.…”