Search Results (25)

Defect engineering can effectively regulate the catalytic activity of single-atom catalysts anchored on the graphene substrate. Based on graphene with topological defects consisting of 5,7-membered carbon rings, we designed and investigated twenty transition metal single-atom catalysts TM-N₄-C57 (TM = Sc~Cu, Zr~Mo, Ru, Rh, Hf~Ir) for electrocatalytic nitrogen reduction reaction (NRR) using density functional theory (DFT) calculations. Employing a screening strategy that considers binding energy, N₂ adsorption, catalytic activity, selectivity, and thermal stability, we ultimately screened out two electrocatalysts (Mo-N₄-C57 and W-N₄-C57) with excellent catalytic activity and selectivity. The NRR pathways on these two catalysts proceed through distal and consecutive pathways, with limiting potentials of −0.19 and −0.53 V for Mo-N₄-C57 and W-N₄-C57, respectively. The activity origin was elucidated through the analysis of partial density of states (PDOS) and crystal orbital Hamilton populations (COHP), suggesting that the interaction between Mo and NH₂ in the *NH₂ intermediate is relatively weak. An excellent linear relationship between U_L and ICOHP has been identified, suggesting it as a descriptor. This work provides a theoretical basis for designing efficient NRR catalysts with modified second coordination spheres. Full article

Rechargeable aqueous Zn-MnO₂ batteries are positioned as a highly promising candidate for next-generation energy storage, owing to their compelling combination of economic viability, inherent safety, exceptional capacity (with a theoretical value of ≈308 mAh·g⁻¹), and eco-sustainability. However, this system still faces multiple critical challenges that hinder its practical application, primarily including the ambiguous energy storage reaction mechanism (e.g., unresolved debates on core issues such as ion transport pathways and phase transition kinetics), dendrite growth and side reactions (e.g., the hydrogen evolution reaction and corrosion reaction) on the metallic Zn anode, inadequate intrinsic electrical conductivity of MnO₂ cathodes (≈10⁻⁵ S·cm⁻¹), active material dissolution, and structural collapse. This review begins by systematically summarizing the prevailing theoretical models that describe the energy storage reactions in Zn-Mn batteries, categorizing them into the Zn²⁺ insertion/extraction model, the conversion reaction involving MnO_x dissolution–deposition, and the hybrid mechanism of H⁺/Zn²⁺ co-intercalation. Subsequently, we present a comprehensive discussion on Zn anode protection strategies, such as surface protective layer construction, 3D structure design, and electrolyte additive regulation. Furthermore, we focus on analyzing the performance optimization strategies for MnO₂ cathodes, covering key pathways including metal ion doping (e.g., introduction of heteroions such as Al³⁺ and Ni²⁺), defect engineering (oxygen vacancy/cation vacancy regulation), structural topology optimization (layered/tunnel-type structure design), and composite modification with high-conductivity substrates (e.g., carbon nanotubes and graphene). Therefore, this review aims to establish a theoretical foundation and offer practical guidance for advancing both fundamental research and practical engineering of Zn-manganese oxide secondary batteries. Full article

With the rapid development of high-speed imaging, aerospace, and telecommunications, high-performance photodetectors across a broadband spectrum are urgently demanded. Due to abundant surface configurations and exceptional electronic properties, two-dimensional (2D) materials are considered as ideal candidates for broadband photodetection applications. However, broadband photodetectors with both high responsivity and fast response time remain a challenging issue for all the researchers. This review paper is organized as follows. Introduction introduces the fundamental properties and broadband photodetection performances of transition metal dichalcogenides (TMDCs), perovskites, topological insulators, graphene, and black phosphorus (BP). This section provides an in-depth analysis of their unique optoelectronic properties and probes the intrinsic physical mechanism of broadband detection. In Two-Dimensional Material-Based Broadband Photodetectors, some innovative strategies are given to expand the detection wavelength range of 2D material-based photodetectors and enhance their overall performances. Among them, chemical doping, defect engineering, constructing heterostructures, and strain engineering methods are found to be more effective for improving their photodetection performances. The last section addresses the challenges and future prospects of 2D material-based broadband photodetectors. Furthermore, to meet the practical requirements for very large-scale integration (VLSI) applications, their work reliability, production cost and compatibility with planar technology should be paid much attention. Full article

A switchable enhancement group delay in the terahertz band based on a novel sandwich topology protection structure with graphene is proposed in this paper. The notable phase transition of the reflected beam comes from the topological edge-protected mode excited at the sandwich photonic crystal surface, and the non-trivial topology of the photonic crystal allows the structure to be immune against defects and imperfections, which lays the foundation for the enhancement of group delay in the terahertz band. And the introduction of graphene creates favorable conditions for the reversible switching of positive and negative reflection group delay. Moreover, the reflected group delay can also be flexibly and dynamically controlled by the incident angle. The positive and negative reversible switching reflected group delay proposed in the terahertz band greatly reduces the optical transmission loss and significantly increases the transmission efficiency compared with the traditional metal sandwich structure, which provides a feasible idea for the realization of multi-dimensional manipulation of the wavelength and phase of electromagnetic waves in the terahertz band. The novel scheme is expected to provide potential applications in fields such as optical buffers or ultrafast modulators. Full article

The study of spinning systems plays a question of interest in several research branches in physics. It allows the understanding of simple classical mechanical systems but also provides us with tools to investigate a wide range of phenomena, from condensed matter physics to gravitation and cosmology. In this contribution, we review some remarkable theoretical aspects involving the description of spinning quantum systems. We explore the nonrelativistic and relativistic domains and their respective applications in fields such as graphene physics and topological defects in gravitation. Full article

Despite considerable progress, high-performing durable catalysts operating under large current densities (i.e., >1000 mA/cm²) are still lacking. To discover platinum group metal-free (PGM-free) electrocatalysts for sustainable energy, our research involves investigating layered topological magnetic materials (semiconducting ferromagnets) as highly efficient electrocatalysts for the hydrogen evolution reaction under high current densities and establishes the novel relations between structure and electrochemical property mechanisms. The materials of interest include transition metal trihalides, i.e., CrCl₃, VCl₃, and VI₃, wherein a structural unit, the layered structure, is formed by Cr (or V) atoms sandwiched between two halides (Cl or I), forming a tri-layer. A few layers of quantum crystals were exfoliated (~50−60 nm), encapsulated with graphene, and electrocatalytic HER tests were conducted in acid (0.5M H₂SO₄) and alkaline (1M KOH) electrolytes. We find a reasonable HER activity evolved requiring overpotentials in a range of 30–50 mV under 10 mA cm⁻² and 400−510 mV (0.5M H₂SO₄) and 280−500 mV (1M KOH) under −1000 mA cm⁻². Likewise, the Tafel slopes range from 27 to 36 mV dec⁻¹ (Volmer–Tafel) and 110 to 190 mV dec⁻¹ (Volmer–Herovsky), implying that these mechanisms work at low and high current densities, respectively. Weak interlayer coupling, spontaneous surface oxidation, the presence of a semi-oxide subsurface (e.g., O–CrCl₃), intrinsic Cl (or I) vacancy defects giving rise to in-gap states, electron redistribution (orbital hybridization) affecting the covalency, and sufficiently conductive support interaction lowering the charge transfer resistance endow the optimized adsorption/desorption strength of H^* on active sites and favorable electrocatalytic properties. Such behavior is expedited for bi-/tri-layers while exemplifying the critical role of quantum nature electrocatalysts with defect sites for industrial-relevant conditions. Full article

Optical absorbers based on Tamm plasmon states are known for their simple structure and high operational efficiency. However, these absorbers often have limited absorption channels, and it is challenging to continuously adjust their light absorption rates. Here, we propose a Tamm plasmon state optical absorber composed of a layered stack structure consisting of one-dimensional topological photonic crystals and graphene nano-composite materials. Using the four-by-four transfer matrix method, we investigate the structural relationship of the absorber. Our results reveal that topological interface states (TISs) effectively excite the optical Tamm state (OTS), leading to multiple absorption peaks. This expands the number of absorption channels, with the coupling number of the TIS determining the transmission quality of these channels—a value further adjustable by the period number of the photonic crystals. Tuning the filling factor, refractive index, and thickness of the graphene nano-composite material allows for a wide range of control over the device’s absorption rate, from 0 to 1. Additionally, adjusting the defect layer thickness, incident angle, and Fermi energy enables us to control the absorber’s operational bandwidth and the switching of its absorption effect. This work presents a new approach to expanding the tunability of optoelectronic devices. Full article

The electronic structure of 7/9-AGNR superlattices with up to eight unit cells has been studied by means of state-of-the-art Density Functional Theory (DFT) and also by two model Hamiltonians, the first one including only local interactions (Hubbard model, Hu) while the second one is extended to allow long-range Coulomb interactions (Pariser, Parr and Pople model, PPP). Both are solved within mean field approximation. At this approximation level, our calculations show that 7/9 interfaces are better described by spin non-polarized solutions than by spin-polarized wavefunctions. Consequently, both Hu and PPP Hamiltonians lead to electronic structures characterized by a gap at the Fermi level that diminishes as the size of the system increases. DFT results show similar trends although a detailed analysis of the density of states around the Fermi level shows quantitative differences with both Hu and PPP models. Before improving model Hamiltonians, we interpret the electronic structure obtained by DFT in terms of bands of topological states: topological states localized at the system edges and extended bulk topological states that interact between them due to the long-range Coulomb terms of Hamiltonian. After careful analysis of the interaction among topological states, we find that the discrepancy between ab initio and model Hamiltonians can be resolved considering a screened long-range interaction that is implemented by adding an exponential cutoff to the interaction term of the PPP model. In this way, an adjusted cutoff distance $\lambda =2$ allows a good recovery of DFT results. In view of this, we conclude that the correct description of the density of states around the Fermi level (Dirac point) needs the inclusion of long-range interactions well beyond the Hubbard model but not completely unscreened as is the case for the PPP model. Full article

We investigated gated multilayer graphene with stacking order changes along the armchair direction. We consider that some layers cracked to release shear strain at the stacking domain wall. The energy cones of graphene overlap along the corresponding direction in the k-space, so the topological gapless states from different valleys also overlap. However, these states strongly interact and split due to atomic-scale defects caused by the broken layers, yielding an effective energy gap. We find that for some gate voltages, the gap states cross and the metallic behavior along the stacking domain wall can be restored. In particular cases, a flat band appears at the Fermi energy. We show that for small variations in the gate voltage, the charge occupying this band oscillates between the outer layers. Full article

Graphene sheets are a highly radiation-resistant material for prospective nuclear applications and nanoscale defect engineering. However, the precise mechanism of graphene radiation hardness has remained elusive. In this paper, we study the origin and nature of defects induced by gamma radiation in a graphene rolled-up plane. In order to reduce the environmental influence on graphene and reveal the small effects of gamma rays, we have synthesized a novel graphene-based nanocomposite material containing a bilayer of highly aligned carbon nanotube assemblies that have been decorated by organometallic compounds and suspended on nanoporous Al${}_2$O${}_3$ membranes. The bilayer samples were irradiated by gamma rays from a ${}^{137}$Cs source with a fluence rate of the order of ${10}^5$ m${}^{-2}$s${}^{-1}$. The interaction between the samples and gamma quanta results in the appearance of three characteristic photon escape peaks in the radiation spectra. We explain the mechanism of interaction between the graphene sheets and gamma radiation using a pseudo-Majorana fermion graphene model, which is a quasi-relativistic $N=3$-flavor graphene model with a Majorana-like mass term. This model admits the existence of giant charge carrier currents that are sufficient to neutralize the impact of ionizing radiation. Experimental evidence is provided for the prediction that the 661.7-keV gamma quanta transfer enough energy to the electron subsystem of graphene to bring about the deconfinement of the bound pseudo-Majorana modes and involve C atoms in a vortical motion of the electron density flows in the graphene plane. We explain the radiation hardness of graphene by the topological non-triviality of the pseudo-Majorana fermion configurations comprising the graphene charge carriers. Full article

Self-consistent density functional tight binding (SCC-DFTB) approaches were used to study optimized structures, energy, differential charge density, and Mülliken populations for the (8,0) carbon nanotubes (CNTs) connected to the graphene having different topology defects. Based on the calculations, nine seamless (8,0)CNT-graphenes were selected. For these connected systems, geometric configurations of the graphene and nanotubes were characterized, and the nearest neighbor length of C-C atoms and average length were obtained. The intrinsic energy, energy gap, and chemical potential were analyzed, and they presented apparent differences for different connection modes. Differential charge densities of these connection modes were analyzed to present covalent bonds between the atoms. We have also thoroughly analyzed the Mülliken charge transfer among the C atoms at the junctions. Full article

Extended line defect (ELD) graphene is a two-dimensional (2D) topologically defective graphene with alternate octagonal and quadrilateral carbon rings as basic defective units. This paper reports on the CH₄ adsorption properties of ELD graphene according to the first principles of density functional theory (DFT). The effects on the CH₄ adsorption of ELD graphene when modified by a single Mn atom or two Mn atoms were investigated, respectively. An ELD-42C graphene configuration consisting of 42 C atoms was first constructed. Then, the ELD-42C graphene configuration was used as a substrate, and a Mn-ELD-42C graphene configuration was obtained by modifying it with a single Mn atom. The results showed that the most stable adsorption site for Mn atoms was above the quadrilateral carbon ring. This Mn-ELD-42C graphene configuration could only stably adsorb up to 30 CH₄ molecules on each side, with an average adsorption energy of −0.867 eV/CH₄ and an adsorption capacity of 46.25 wt%. Three 2Mn-ELD-42C graphene configurations were then obtained by modifying the ELD-42C graphene substrate with two Mn atoms. When the two Mn atoms were located on either side of a 2Mn-ELD-42C graphene configuration and above the two octagonal carbon rings adjacent to the same quadrilateral carbon ring, it was able to adsorb up to 40 CH₄ molecules on each side, with an average adsorption energy of −0.862 eV/CH₄ and a CH₄ adsorption capacity of 51.09 wt%. Full article

Recent advances in experimental studies of nanoparticle-driven stabilization of chiral liquid-crystalline phases are highlighted. The stabilization is achieved via the nanoparticles’ assembly in the defect lattices of the soft liquid-crystalline hosts. This is of significant importance for understanding the interactions of nanoparticles with topological defects and for envisioned technological applications. We demonstrate that blue phases are stabilized and twist-grain boundary phases are induced by dispersing surface-functionalized CdSSe quantum dots, spherical Au nanoparticles, as well as MoS₂ nanoplatelets and reduced-graphene oxide nanosheets in chiral liquid crystals. Phase diagrams are shown based on calorimetric and optical measurements. Our findings related to the role of the nanoparticle core composition, size, shape, and surface coating on the stabilization effect are presented, followed by an overview of and comparison with other related studies in the literature. Moreover, the key points of the underlying mechanisms are summarized and prospects in the field are briefly discussed. Full article

Graphene is a two-dimensional material, with exceptional mechanical, electrical, and thermal properties. Graphene-based materials are, therefore, excellent candidates for use in nanocomposites. We investigated reduced graphene oxide (rGO), which is produced easily by oxidizing and exfoliating graphite in calcium silicate hydrate (CSHs) composites, for use in cementitious materials. The density functional theory was used to study the binding of moieties, on the rGO surface (e.g., hydroxyl-OH/rGO and epoxide/rGO groups), to CSH units, such as silicate tetrahedra, calcium ions, and OH groups. The simulations indicate complex interactions between OH/rGO and silicate tetrahedra, involving condensation reactions and selective repairing of the rGO lattice to reform pristine graphene. The condensation reactions even occurred in the presence of calcium ions and hydroxyl groups. In contrast, rGO/CSH interactions remained close to the initial structural models of the epoxy rGO surface. The simulations indicate that specific CSHs, containing rGO with different interfacial topologies, can be manufactured using coatings of either epoxide or hydroxyl groups. The results fill a knowledge gap, by establishing a connection between the chemical compositions of CSH units and rGO, and confirm that a wet chemical method can be used to produce pristine graphene by removing hydroxyl defects from rGO. Full article

A technology for the formation of electrically conductive nanostructures from single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNT), and their hybrids with reduced graphene oxide (rGO) on Si substrate has been developed. Under the action of single pulses of laser irradiation, nanowelding of SWCNT and MWCNT nanotubes with graphene sheets was obtained. Dependences of electromagnetic wave absorption by films of short and long nanotubes with subnanometer and nanometer diameters on wavelength are calculated. It was determined from dependences that absorption maxima of various types of nanotubes are in the wavelength region of about 266 nm. It was found that contact between nanotube and graphene was formed in time up to 400 fs. Formation of networks of SWCNT/MWCNT and their hybrids with rGO at threshold energy densities of 0.3/0.5 J/cm² is shown. With an increase in energy density above the threshold value, formation of amorphous carbon nanoinclusions on the surface of nanotubes was demonstrated. For all films, except the MWCNT film, an increase in defectiveness after laser irradiation was obtained, which is associated with appearance of C–C bonds with neighboring nanotubes or graphene sheets. CNTs played the role of bridges connecting graphene sheets. Laser-synthesized hybrid nanostructures demonstrated the highest hardness compared to pure nanotubes. Maximum hardness (52.7 GPa) was obtained for MWCNT/rGO topology. Regularity of an increase in electrical conductivity of nanostructures after laser irradiation has been established for films made of all nanomaterials. Hybrid structures of nanotubes and graphene sheets have the highest electrical conductivity compared to networks of pure nanotubes. Maximum electrical conductivity was obtained for MWCNT/rGO hybrid structure (~22.6 kS/m). Networks of nanotubes and CNT/rGO hybrids can be used to form strong electrically conductive interconnections in nanoelectronics, as well as to create components for flexible electronics and bioelectronics, including intelligent wearable devices (IWDs). Full article