Zigzag Edges Research Articles

Defect-Engineered Mesoporous Undoped Carbon Nanoribbons for Benchmark Oxygen Reduction Reaction.

For large-scale fuel cell applications, it is significant to replace expensive Pt-based oxygenreductionreaction (ORR) electrocatalysts with nonprecious metal- or metal-free carbon-based catalysts with high activity. However, it is still challenging to deeply understand the role of intrinsic defects and the origin of ORR activity in pure nanocarbon. Therefore, a novel self-assembly and a pyrolysis strategy to fabricate defect-rich mesoporous carbon nanoribbons are presented. Due to the effective regulation of nanoarchitecture, a vast number of defective catalytic sites (edge defects and holes) are exposed, which thereby enhances the electron transfer kinetics and catalytic activity. Such undoped nanoribbons display a large half-wave potential of 0.837V, excellent long-term stability, and exceptional methanol tolerance, surpassing the most undoped ORR catalysts and the commercial Pt/C (20wt.%) catalyst. Structural characterizations and density functional theory (DFT) calculations confirm that the zigzag edge defects and the armchair pentagon at the hole defect are responsible for outstanding ORR performance.

Magnetism in Nonplanar Zigzag Edge Termini of Graphene Nanoribbons

AbstractGraphene nanoribbons (GNRs) and nanographenes synthesized by on‐surface reactions using tailor‐made molecular precursors offer an ideal playground for a study of magnetism towards nano‐spintronics. Although the zigzag edge of GNRs has been known to host magnetism, the underlying metal substrates usually veil the edge‐induced Kondo effect. Here, we report the on‐surface synthesis of unprecedented, π‐extended 7‐armchair GNRs using 7‐bromo‐12‐(10‐bromoanthracen‐9‐yl)tetraphene as the precursor. Characterization by scanning tunneling microscopy/spectroscopy revealed unique rearrangement reactions leading to pentagon‐ or pentagon/heptagon‐incorporated, nonplanar zigzag termini, which demonstrated Kondo resonances even on bare Au(111). Density functional theory calculations indicate that the nonplanar structure significantly reduces the interaction between the zigzag terminus and the Au(111) surface, leading to a recovery of the spin localization of the zigzag edge. Such a distortion of planar GNR structures offers a degree of freedom to control the magnetism on metal substrates.

Magnetism in Nonplanar Zigzag Edge Termini of Graphene Nanoribbons.

Graphene nanoribbons (GNRs) and nanographenes synthesized by on-surface reaction using tailor-made molecular precursors offer an ideal playground for a study of magnetism towards nano-spintronics. Although the zigzag edge of GNRs has been known to host magnetism, underlying metal substrates usually veil the edge-induced Kondo effect. Here, we report the on-surface synthesis of unprecedented, π-extended 7-armchair GNRs using 7-bromo-12-(10-bromoanthracen-9-yl)tetraphene as the precursor. Characterizations by scanning tunneling microscopy/spectroscopy revealed unique rearrangement reactions leading to pentagon- or pentagon/heptagon-incorporated, nonplanar zigzag termini, which demonstrated Kondo resonance even on bare Au(111). Density functional theory calculations indicate that the nonplanar structure significantly reduces the interaction between the zigzag terminus and the Au(111), leading to a recovery of the spin localization of the zigzag edge. Such distortion of planar GNR structures offers a degree of freedom to control the magnetism on metal substrates.

Zigzag Edge States in Graphene in the Presence of In‐Plane Electric Field

Herein, the edge states in a finite‐width graphene ribbon and a semi‐infinite geometry subject to a perpendicular magnetic field and an in‐plane electric field, applied perpendicular to a zigzag edge, are explored. To accomplish this, a combination of analytic and numerical methods within the framework of low‐energy effective theory is employed. Both the gapless and gapped Dirac fermions in graphene are considered. It is found that a surface mode localized at the zigzag edge remains dispersionless even in the presence of electric field. This is shown analytically by employing Darwin's expansion of the parabolic cylinder functions of large order and argument.

Multiphoton excitation and high harmonic generation in rectangular graphene quantum dot

The multiphoton excitation and high harmonic generation (HHG) processes are considered using the microscopic quantum theory of nonlinear interaction of strong coherent electromagnetic (EM) radiation with rectangular graphene quantum dot (RGQD). The dynamic Hartree–Fock approximation is developed for the consideration of the quantum dot-laser field nonlinear interaction at the nonadiabatic multiphoton excitation regime. The many-body Coulomb interaction is described in the extended Hubbard approximation. By numerical results, we show the significance of the RGQD lateral size, shape, and EM wavefield orientation in RGQD of the zigzag edge compear to the armchair edge in the HHG process allowing for increasing the cutoff photon energy and the quantum yield of higher harmonics. The differences via edge on the elongated side of the RGQD have been explained by the investigation of the dipole momentum in both cases. Numerical results have shown that the HHG spectra have a strong anisotropy depending on the orientation of the laser wave, and the cutoff photon energy shifts toward blue with an increase in the transverse size of the RGQD.

Unconventional Self-Reconstructed Trimer-like Metal Zigzag Edge of 1T-Phase Transition Metal Dichalcogenides

Undercoordination-induced slight bond contraction of the pristine edge is a conventional edge self-reconstructed pattern in two-dimensional materials that generally cannot drive the edge into its ground state. Despite reports of unconventional edge self-reconstructed patterns of 1H-phase transition metal dichalcogenides (TMDCs), there have been no reports of sister 1T-phase TMDCs. Here, we predict an unconventional (2 × 1) edge self-reconstructed pattern for 1T-TMDCs by considering 1T-TiTe2. A novel self-reconstructed trimer-like metal zigzag edge (TMZ edge) with one-dimensional metal atomic chains and Ti3 trimers is uncovered. Its metal triatomic 3d orbital coupling leads to Ti3 trimerization. This TMZ edge occurs in group IV, V, and X 1T-TMDCs and has an energetic advantage far beyond conventional bond contraction. The unique triatomic synergistic effect results in better catalysis of the hydrogen evolution reaction (HER) for the 1T-TMDCs than with commercial platinum-based catalysts. This study provides a new strategy for maximizing the HER catalytic efficiency of 1T-TMDCs by using atomic edge engineering.

Tailoring carbon nanotubes quickly into graphene nanoribbons along axis-direction via dynamic magnetic flux template

So far, the method of top-down preparing graphene nanoribbons by etching of carbon nanotubes (CNTs) mainly relies on the catalytic reaction of Fe, Co, and Ni nanoparticles. However, etching cannot be guaranteed along the CNT axis only. In this study, Ti3AlC2 is decomposed into liquid aluminum in the dynamic magnetic flux template to catalyze the growth of multiwalled carbon nanotubes (MWCNTs). Successively, the obtained MWCNTs are etched in-situ by rutile TiO2 particles to generate multilayered graphene nanoribbons (MLGNRs). Thus-obtained nanoribbons will create zigzag edges full of short-range order segment, demonstrating a spin glass state. This work has paved a new way for a top-down approach to create MLGNRs by tailoring MWCNTs along axis direction only using dynamic magnetic flux template.

Circumcoronenes

AbstractCircumcoronene, a hexagonal graphene fragment with six zigzag edges, has been the focus of theoretical studies for many years, but its synthesis in solution has remained a challenge. In this study, we present a facile method for synthesizing three derivatives of circumcoronene using Brønsted/Lewis acid‐mediated cyclization of vinyl ether or alkyne. Their structures were confirmed through X‐ray crystallographic analysis. Bond length analysis, NMR measurement, and theoretical calculations showed that circumcoronene mostly follows Clar's bonding model and exhibits dominant local aromaticity. Its absorption and emission spectra are similar to those of the smaller hexagonal coronene due to its six‐fold symmetry.

Circumcoronenes.

Circumcoronene, a hexagonal graphene fragment with six zigzag edges, has been the focus of theoretical studies for many years, but its synthesis in solution has remained a challenge. In this study, we present a facile method for synthesizing three derivatives of circumcoronene using Brønsted/Lewis acid-mediated cyclization of vinyl ether or alkyne. Their structures were confirmed through X-ray crystallographic analysis. Bond length analysis, NMR measurement, and theoretical calculations showed that circumcoronene mostly follows Clar's bonding model and exhibits dominant local aromaticity. Its absorption and emission spectra are similar to those of the smaller hexagonal coronene due to its six-fold symmetry.

Terminal Atom-Controlled Etching of 2D-TMDs.

The controlled etching of 2D transition metal dichalcogenides (2D-TMDs) is critical to understanding the growth mechanisms of 2D materials and patterning 2D materials but remains a major comprehensive challenge. Here, a rational strategy to control the terminal atoms of 2D-TMDs etched holes is reported. Using laser irradiation combined with an improved anisotropic thermal etching process under a determined atmosphere, terminal atom-controlled etched hole arrays are created on 2D-TMDs. By adjusting the gas atmosphere during the thermal etching stage, triangular etched hole arrays terminated by the tungstenzigzag(W-ZZ) edge (in an Ar/H2 atmosphere), hexagonal etched hole arrays terminated alternately by the W-ZZ edge and sulfur(selenium)zigzag(S-ZZ orSe-ZZ) edge (in a pure Ar atmosphere), and triangular etched hole arrays terminated by the S-ZZ (Se-ZZ) edge (in an Ar/sulfur [selenium] vapor atmosphere) can be obtained. Density functional theory reveals the forming energy of different edges and the different activities of metal atoms and chalcogenide atoms under different atmospheres, which determine the terminal atoms of the holes. This work may enhance the understanding of the etching and growth of 2D-TMDs. The 2D-TMDs hole arrays constructed by this work may have important applications in catalysis, nonlinear optics, spintronics, and large-scale integrated circuits.

Effect of the Position of Amine Groups on the CO2, CH4, and H2 Adsorption Performance of Graphene Nanoflakes

CO2 separation from CO2/CH4 and CO2/H2 mixtures is essential in H2 production from biogas. Although amine-functionalized carbon materials are excellent candidates for selective CO2 adsorption, their adsorption performance depends on the amine edge position, which requires further clarification. Herein, 19 graphene nanoflakes (GNFs) bearing two amines at various positions on the zigzag, corner, and armchair edges were evaluated. All structures exhibited better CO2 adsorption compared to CH4 and H2. In the GNFs with isolated amines, only one main bond (H2N–CO2) was involved in CO2 adsorption, which was influenced by charge transfer from the GNFs to CO2. GNFs with adjacent amines had an additional hydrogen bond (H2N–CO2) that became stronger with decreasing steric hindrance. The CO2 adsorption performance of amines decreased as the number of methyl groups on the nitrogen increased, which interfered with CO2 adsorption. The presence of H2O hindered the interaction of amines and CO2 owing to the strong hydrogen bond between H2O and amines.

Orbital magnetoelectric effect in nanoribbons of transition metal dichalcogenides

The orbital magnetoelectric effect (OME) generically refers to the appearance of an orbital magnetization induced by an applied electric field. Here, we show that nanoribbons of transition metal dichalcogenides (TMDs) with zigzag (ZZ) edges may exhibit a sizeable OME activated by an electric field applied along the ribbons' axis. We examine nanoribbons extracted from a monolayer (1L) and a bilayer (2L) of MoS$_2$ in the trigonal (H) structural phase. Transverse profiles of the induced orbital angular momentum accumulations are calculated to first order in the longitudinally applied electric field. Our results show that close to the nanoribbon's edge-state crossings energy, the orbital angular momentum accumulations take place mainly around the ribbons' edges. They have two contributions: one arising from the orbital Hall effect (OHE) and the other consists in the OME. The former is transversely anti-symmetric with respect to the principal axis of the nanoribbon, whereas the latter is symmetric, and hence responsible for the resultant orbital magnetization induced in the system. We found that the orbital accumulation originating from the OHE for the 1L-nanoribbon is approximately half that of a 2L-nanoribbon. Furthermore, while the OME can reach fairly high values in 1L-TMD nanoribbons, it vanishes in the 2L ones that preserve spatial inversion symmetry.The microscopic features that justify our findings are also discussed.

Field-Effect Tunneling between Quantum Valley Hall Edge States and Topological Transistors Based on Bilayer Graphene

We study the tunneling effect between quantum valley Hall edge states under an applied electric field in bilayer graphene containing gaps. A topological transistor based on this tunneling effect is proposed. In the on state of the transistor, the quantum valley Hall edge state along one bilayer-graphene zigzag edge can tunnel to the other edge under an electric field. In the off state without the electric field, the edge state cannot tunnel to the other edge and should be reflected by the top armchair edge and retrace the route along the same zigzag edge. The performance of the transistor is shown to be robust against long-range impurities. Compared with the previous transistor based on quantum spin Hall edge states [Xu et al. Phys. Rev. Lett. 123, 206801 (2019)], this transistor based on quantum valley Hall edge states has the advantages that it does not need a ferromagnetic gate to bridge the gap in the edge states and the conductance is robust against both nonmagnetic and magnetic impurities.

Electronic Properties of Single‐Layer and Bilayer Graphene Nanoribbons

Herein, a tight‐binding description is utilized to investigate electronic structures and density of states of single‐layer (SL) and bilayer (BL) graphene ribbons with and without the influence of external electric fields. Analyses are implemented to reveal the similarity and difference among electronic properties of three types of structures (specifically SL and BL ribbons with AA and AB stackings). Moreover, both armchair and zigzag edge orientations are considered. It is indicated in the results that variation in electronic properties of these structures in the presence of external electric fields depends on both structural form and edge orientation. The following two points are demonstrated: 1) a transverse field has a significant effect on adjusting bandgap of the zigzag configurations, whereas a vertical electric field has a distinct impact on energy bands of armchair edge structures, and 2) among considered structures, AB‐stacking BL ribbons are invariably the structures that are most strongly influenced by external fields. Interestingly, AB‐stacking BL ribbons are also capable of enlarging bandgap with both edge terminations. Herein, an insight into how the electronic structure and charge distribution of both SL and BL graphene nanoribbons can be controlled not only in armchair but also in zigzag edge terminations using electric stimulants is provided by the results.

Kinetics effect of hydrogen passivation on the zigzag edge growth of h-BN

Edge kinetics in 2D structures has been a key to understanding the growth. In this paper, the effect of hydrogen passivation on the growth of hexagonal boron nitride (h-BN) was studied. Without hydrogen, the filling process of the gap on bare edges of h-BN is difficult because of the formation of dimers that distorts the edge. With hydrogen passivation, such difficulty can be largely reduced. In addition, hydrogen passivation can reduce the edge bending to the substrate. In summary, the amount of hydrogen passivation during the growth is the long-ignored parameter and can be the key to a good crystal quality.

Scanning gate microscopy in graphene nanostructures

The conductance of graphene nanoribbons and nanoconstrictions under the effect of a scanning gate microscopy tip is systematically studied. Using a scattering approach for noninvasive probes, the first- and second-order conductance corrections caused by the tip potential disturbance are expressed explicitly in terms of the scattering states of the unperturbed structure. Numerical calculations confirm the perturbative results, showing that the second-order term prevails in the conductance plateaus, exhibiting a universal scaling law for armchair graphene strips. For stronger tips, at specific probe potential widths and strengths beyond the perturbative regime, the conductance corrections reveal the appearance of resonances originated from states trapped below the tip. The zero-transverse-energy mode of an armchair metallic strip is shown to be insensitive to the long-range electrostatic potential of the probe. For nanoconstrictions defined on a strip, scanning gate microscopy allows to get insight into the breakdown of conductance quantization. The first-order correction generically dominates at low tip strength, while for Fermi energies associated with faint conductance plateaus, the second-order correction becomes dominant for relatively small potential tip strengths. In accordance with the spatial dependence of the partial local density of states, the largest tip effect occurs in the central part of the constriction, close to the edges. Nanoribbons and nanoconstrictions with zigzag edges exhibit a similar response as in the case of armchair nanostructures, except when the intervalley coupling induced by the tip potential destroys the chiral edge states.

Modification of micro-crystalline graphite and carbon black by acetone, toluene, and phenol.

The chemical interactions of two types of graphite and two types of carbon black (CB) with acetone, toluene, and phenol were studied in order to evaluate the influence of chemical treatment on the structure and morphology of the carbon phases. The experimental treatment of carbon phases was carried out at room temperature for 1 hour. The chemical and phase composition were studied by x-ray photoelectron (XP) and Raman spectroscopies, while the morphology and structure were determined by powder x-ray diffraction, as well as transmission electron microscopy techniques. To shed light on the most probable explanation of the observed results, we performed simulations and calculations of the binding energies of acetone, toluene, and phenol with model carbon phases: a perfect graphene sheet and a defective graphene sheet containing various structural defects (vacancies as well as zigzag and armchair edges). Simulations show that all non-covalent and most covalent coupling reactions are exothermic, with acetone coupling having the higher calorimetric effect. Based on the results of the simulations and the XP spectroscopy measurements, the probable reactions taking place during the respective treatments are outlined. The conducted studies (both theoretical and experimental) show that the treatment of graphite powders and CB with acetone, toluene, or phenol can be used as a preliminary stage of their modification and/or functionalization, including their conversion into graphene-like (defective graphene, reduced graphene oxide, and/or graphene oxide) phases. For example, the treatment of SPHERON 5000 with acetone significantly facilitates their subsequent modification with laser radiation to graphene-like phases.

Zigzag Graphene Nanoribbons and Confluent Supersymmetry

We studied the behavior of charge carriers in graphene nanoribbons with zigzag edges. We start from free nanoribbons, and by using second-order confluent supersymmetry, we added external magnetic fields perpendicular to the graphene layer. The technique allows us to obtain explicit expressions for the solution of the Dirac equation and gives the transcendental equations that must be solved to obtain the energy spectrum.

Emergent magnetic-nonmagnetic transition in strain-tuned zigzag-edged PtSe2 nanoribbon

Magnetic responses in nonmagnetic transition metal dichalcogenides (TMDs) via reduced dimension and defect engineering continue to bring forth emergent properties and has revolutionized important technologies such as data storage and magnetic sensing. Using the first-principles calculation, we investigate the zigzag-edged ${\mathrm{PtSe}}_{2}$ (zz-${\mathrm{PtSe}}_{2}$) nanoribbon with a sizable magnetization solely at the zigzag edges and a remarkable magnetic-nonmagnetic switching induced by a small compressive uniaxial strain of about \ensuremath{-}2%. We further interpret the sudden disappearance of the magnetization by a simple but clear model simulation considering the localized quasi-one-dimensional magnetic channels mediated by metallic backgrounds along the edges. Such newly proposed strain-controlled magnetic transition through band structure engineering highlights zz-${\mathrm{PtSe}}_{2}$ as a unique candidate for controllable TMD-based one-dimensional magnets with promising advances in fundamental physics and technological opportunities in spintronics, computing, and sensors.

BN-Doped Carbon Nanotubes and Nanoribbons as Nonlinear-Optical Functional Materials for Application in Second-Order Nonlinear Optics

Pure carbon-based nanomaterials with good π conjugation and thermal stability, e.g., nanotubes and nanoribbons, have long served as promising conjugated materials for application in second-order nonlinear-optical (NLO) devices but suffer from two inherent structural problems: weak polarity (or even nonpolarity) and high chemical reactivity ascribed to zigzag edge states. In the present work, boron nitride (BN) chains are used to divide carbon nanotubes and nanoribbons, forming a functional block to tune the electronic structure, and thus induce charge redistribution or modify the molecular energy gap for second-order NLO materials or integrated electronic materials. A balance between the electronic kinetic stability and second-order NLO properties is established by structural manipulation. The strong second-order NLO responses in the visible and near-infrared regions make these hybridized carbon-based molecules potential NLO materials for applications in biological nonlinear optics. The application of BN to tune the electronic structure of carbon nanomaterials paves a path for fabricating nanoelectronic and nano-NLO devices.