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γ‐Graphyne (GY), an emerging carbon allotrope, is envisioned to offer various alluring properties and broad applicability. While significant progress has been made in the synthesis of GY over recent decades, its widespread application hinges on developing efficient, scalable, and accessible synthetic methods for the production of GY and its derivatives. Here we report a facile metal‐free nucleophilic crosslinking method using wet chemistry for fast gram‐scale production of GY and its derivatives. This synthesis method involves the aromatic nucleophilic substitution reactions between fluoro‐(hetero)arenes and alkynyl silanes in the presence of a catalytic amount of tetrabutylammonium fluoride, where the fluoride plays a crucial role in removing protective groups from alkynyl silanes and generating reactive alkynylides. Our comprehensive analysis of the as‐prepared GY reveals a layered structure, characterized by the presence of the C(sp)−C(sp2) bond. The synthetic strategy shows remarkable tolerance to various functional groups and enables the preparation of diverse F‐/N‐rich GY derivatives, using electron‐deficient fluoro‐substituted (hetero)arenes as precursors. The feasibility of producing GY and derivatives from fluorinated (hetero)arenes through the metal‐free, scalable, and cost‐effective approach paves the way for broad applications of GY and may inspire the development of new carbon materials. [ABSTRACT FROM AUTHOR]

B3LYP was employed as a density functional to inspect the impact of Mn doping on the ability of graphyne (Gr) in the delivery of the propylthiouracil (PTU) drug. The interaction between the pure Gr and PTU was weak. Doping of the Mn metal into the Gr surface raised the PTU adhesion energy from −6.1 to −28.3 kcal mol−1, and PTU prefers to attach through its O atom to an Mn of the Mn-doped Gr (Mn@Gr). The analysis of partial density-of-states demonstrated that Mn substantially contributes to generating the virtual orbitals of Mn@Gr. It indicates the suitability of Mn, in contrast to the C atoms of Gr, for the nucleophilic attack. In addition to substantial energy release, the electronic properties of Mn@Gr were appreciably sensitive to the attachment of PTU, making it possible for recognizing the trajectory of the drug. A drug release mechanism was provided in cancer tissues, demonstrating that in cancer cells with a low pH, PTU and Mn@Gr were protonated significantly, thus separating PTU from the surface of Gr. Finally, there was a change in the reaction mechanism of PTU with Mn@Gr from covalent bonding in the natural environment to the H-bonding in the acidic environment of cancerous cells. [ABSTRACT FROM AUTHOR]

NanoTube Construct is a web tool for the digital construction of nanotubes based on real and hypothetical single-layer materials including carbon-based materials such as graphene, graphane, graphyne polymorphs, graphidiyene and non-carbon materials such as silicene, germanene, boron nitride, hexagonal bilayer silica, haeckelite silica, molybdene disulfide and tungsten disulfide. Contrary to other available tools, NanoTube Construct has the following features: a) it is not limited to zero thickness materials with specific symmetry, b) it applies energy minimisation to the geometrically constructed Nanotubes to generate realistic ones, c) it derives atomistic descriptors (e.g., the average potential energy per atom, the average coordination number, etc.), d) it provides the primitive unit cell of the constructed Nanotube which corresponds to the selected rolling vector (i.e., the direction in which the starting nanosheet is rolled to form a tube), e) it calculates whether the Nanotube or its corresponding nanosheet is more energetically stable and f) it allows negative chirality indexes. Application of NanoTube Construct for the construction of energy minimised graphane and molybdenum disulfide nanotubes are presented, showcasing the tool's capability. NanoTube Construct is freely accessible through the Enalos Cloud Platform (https://enaloscloud.novamechanics.com/diagonal/nanotube/).

Topological indices are mathematical descriptors of the structure of a molecule that can be used to predict its properties. They are derived from the graph theory, which describes the topology of a molecule and its connectivity. The main objective is mathematical modeling and topological properties of Y-graphyne. Current research focuses on two structures made from hexagonal honeycomb graphite lattices named triangular Y-graphyne and triangular Y-graphyne chains. The authors have simultaneously computed the first and second Reverse Zagreb indices, reverse hyper-Zagreb indices, and their polynomials. This research also derives mathematical closed-form formulas for some of its fundamental degree-based molecular descriptors. Researchers have been trying to synthesize a novel carbon form called Graphyne. For over a decade but with no success. Recently, some researchers have made a breakthrough in generating Carbons elusive allotrope and solved a long-standing problem in carbon materials. This wonder material is created to rival the conductivity of graphene but with control. These results opened new ways of research in the fields of semiconductors, electronics and optics. Furthermore, graphical and tabular results will help to investigate the structure-property relationships in γ-graphyne. [ABSTRACT FROM AUTHOR]

Graphyne-based nanotubes are cylindrical structures made up of a single layer of graphyne that has been rolled into a tube. These one-dimensional structures are constructed from carbon atoms with both sp and sp2 hybridization. The common graphene-based carbon nanotubes, and graphyne-based nanotubes including α-, β-, γ-, α2-, 6,6,12-, and δ-graphyne nanotubes are introduced. The atomic structures and electronic characteristics of these tubes are reviewed. The electronic band structures and density of states calculated by density functional theory are presented. The nanotubes with different types and chiralities display either metallic or semiconducting characteristics. The variety of structures and electronic properties of these nanotubes make them extremely hopeful for applications, especially in nanoelectronic devices such as field emission transistors, sensors, nanoelectromechanical systems, super capacitors, energy and data storage devices. [ABSTRACT FROM AUTHOR]

Electrocatalytic nitrogen reduction reaction (NRR) is a promising technology for ammonia synthesis under environmental conditions due to its simplicity of operation, high energy conversion, and environmental friendliness. While development of an efficient and stable electrocatalyst is one of the remaining key challenges. In this paper, the electrocatalytic performance of single Ru atoms anchored in Bn-doped graphyne (RuBn@GY) is systematically investigated using density functional theory (DFT) calculations. The results show that RuB@GY is a highly efficient NRR electrocatalyst with a distal and alternating mechanism considered to be the most active catalytic pathway, with a limiting potential of only − 0.53 V. Overall, our study facilitates the NRR reaction by controlling the number and position of the doped B atoms to reduce the limiting potential, and this work provides theoretical guidance for the further development of highly active and stable single-atom catalysts (SACs). Electrocatalytic nitrogen reduction reaction (NRR) is a promising technology for ammonia synthesis under environmental conditions due to its simplicity of operation, high energy conversion, and environmental friendliness. [ABSTRACT FROM AUTHOR]

We unveil that the holey graphyne (HGY), a two-dimensional carbon allotrope where benzene rings are connected by two −C≡C− bonds fabricated recently in a bottom-up way, exhibits topological electronic states. Using first-principles calculations and Wannier tight-binding modeling, we discover a higher-order topological invariant associated with C 2 symmetry of the material, and show that the resultant corner modes appear in nanoflakes matching to the structure of precursor reported previously, which are ready for direct experimental observations. In addition, we find that a band inversion between emergent g -like and h -like orbitals gives rise to a nontrivial topology characterized by Z 2 invariant protected by an energy gap as large as 0.52 eV, manifesting helical edge states mimicking those in the prominent quantum spin Hall effect, which can be accessed experimentally after hydrogenation in HGY. We hope these findings trigger interests towards exploring the topological electronic states in HGY and related future electronics applications. [ABSTRACT FROM AUTHOR]

A substantial amount of scholarly inquiry has focused on the advancement of innovative methodologies for drug administration. In this research, both graphyne (GY) and BN-analog GY (BNY) nanosheets are presented. The study focuses on the carbon allotrope GY. Density Functional Theory (DFT) calculations were used to assess how GY, BNY, and the anticancer drug ciclopirox (CPX) interact with one another. It was observed that the inherent capability of pristine GY to augment CPX adsorption is intensified by the involvement of nitrogen (N) and boron (B) atoms. Furthermore, examination using Ultraviolet–Visible (UV-Vis) analysis exhibited a shift towards less energetic states, corresponding to longer wavelengths. Moreover, the interaction between CPX and BNY displayed chemical reactivity, rendering it conducive for forming bonds at the adsorption site. Additionally, a thorough investigation via the Atoms-In-Molecules (AIM) analysis furnished a more profound comprehension of the associations between the drug and the nanosheet. Notably robust connections between CPX and BNY were detected. As a consequence, the potential of BNY to function as a viable transporter for CPX in the realm of drug delivery was substantiated. [ABSTRACT FROM AUTHOR]

The recent experimental synthesis of superalkalis has motivated us to investigate their potential application on hydrogen storage. The hydrogen adsorption mechanism of superalkali decorated graphyne were investigated by density functional theory calculations. The adsorption properties of NLi 4 and NLi 3 Na on graphyne have been investigated. The large binding energy between the superalkalis and graphyne nanosheet demonstrated that the NLi 4 and NLi 3 Na could be dispersed uniformly on graphyne without any clustering. Each NLi 4 and NLi 3 Na on graphyne can store ten and six H 2 molecules, respectively. The charge transfer, electrostatic effect, and the orbital hybridization between H, Li, and C enhanced the hydrogen adsorption energy of NLi 4 decorated graphyne. The 4NLi 4 /G and 4NLi 3 Na/G complexes can store 40 and 24H 2 molecules with a moderate average adsorption energy of −0.283 eV and −0.289 eV, resulting in the hydrogen storage density of 9.78 w. t. % and 5.65 w. t. %, respectively, surpassing the target of US DOE. These results suggested that superalkalis decorated graphyne could be considered as a promising candidate for hydrogen storage. • Strong bond and electrostatic repulsion hinder the clustering of NLi 4. • The 4NLi 4 /G storing 40H 2 with the average adsorption energy of −0.283 eV. • Each NLi 4 on graphyne capture ten H 2. • The T D ensure it to be promising candidate at operating condition. [ABSTRACT FROM AUTHOR]

Topological indices are mathematical descriptors of the structure of a molecule that can be used to predict its properties. They are derived from the graph theory, which describes the topology of a molecule and its connectivity. The main objective is mathematical modeling and topological properties of ϒ-graphyne. Current research focuses on two structures made from hexagonal honeycomb graphite lattices named triangular ϒ-graphyne and triangular ϒ-graphyne chains. The authors have simultaneously computed the first and second Reverse Zagreb indices, reverse hyper-Zagreb indices, and their polynomials. This research also derives mathematical closed-form formulas for some of its fundamental degree-based molecular descriptors. Researchers have been trying to synthesize a novel carbon form called Graphyne. For over a decade but with no success. Recently, some researchers have made a breakthrough in generating Carbons elusive allotrope and solved a long-standing problem in carbon materials. This wonder material is created to rival the conductivity of graphene but with control. These results opened new ways of research in the fields of semiconductors, electronics and optics. Furthermore, graphical and tabular results will help to investigate the structure-property relationships in γ-graphyne.

Gas adsorption on one-atom-thick membranes is a growing technology for separation applications owing to its excellent energy efficiency. Herein, we investigate the adsorption of the noble gases, Ne, Ar and Kr on graphynes (GYs), a novel class of one-atom-thick carbon membranes using a swarm intelligence technique, namely particle swarm optimization (PSO). Modeling the adsorption of noble gas clusters on two-dimensional substrates requires a thorough examination of the energy landscape. The high dimensionality of the problem makes it tricky to employ ab initio methods for such studies, necessitating the use of a metaheuristic global optimization technique such as PSO. We explored the adsorption of 1–30 atoms of Ne, Ar and Kr on α-, β-, γ- and rhombic-GYs to predict the most suitable form of GY for the adsorption of each of the gases. Employing the dispersion-corrected density functional theory (DFT-D) data for the adsorption of single gas atoms as the reference data, we parametrized two empirical pairwise potentials, namely, Lennard-Jones (LJ) and improved Lennard-Jones (ILJ) potentials. We then analyzed the growth pattern as well as the energetics of adsorption using the parametrized potentials, in combination with the PSO technique, which enabled us to predict the best possible membrane for the adsorption of the noble gases: α-GY for Ne and γ-GY for Ar and Kr. The accuracy of our modeling approach is further validated against DFT-D computations thereby establishing that PSO, when combined with the ILJ potential, can serve as a computationally feasible approach for modeling gas adsorption on GYs.

The search for new materials for electronic or nanomechanical devices is of great importance today. Such 2D nanostructures as graphene have attracted much attention due to their unique physical and mechanical properties. Graphynes are a class of new nanostructures with sp- and sp2-hybridized carbon atoms arranged in a crystal lattice, which exhibit high strength and attractive electronic properties. In the present work, molecular dynamics is used to study the mechanical behavior of graphynes under tension at 0 K. Graphene, four graphynes β1-, β3-, γ1-, γ2- graphynes, and γ1‑graphdiyne were considered. Tensile deformation is applied in such a way to allow wrinkling of the 2D structure. Two deformation mechanisms were found for all the considered structures: bond elongation and rotation combined with wrinkling/flattening of the 2D structure. It was found, that the higher the density of the structure, the higher the ultimate tensile strength under tension. Initially, weaker bonds between carbon atoms contributed to the tensile deformation, while at high strain, acetylenic bonds began to contribute. Changes in the valent angles also contribute significantly to the tensile behavior at different deformation stages, becoming critical at the final deformation stage. Tensile deformation is accompanied by the continuous wrinkling and then flattening of the 2D structure. Understanding the deformation behavior of such a novel structures as graphynes is of great importance for their future application in new electronic devices. [ABSTRACT FROM AUTHOR]

The electrical and electronic characteristics of three graphyne allotropes (10-18-6 graphyne, 10-12-18-6 graphyne, and 12-14-18-6 graphyne) were examined based on first-principles calculations using the generalized gradient approximation. The changes in system characteristics when carbon atoms were replaced with boron and nitrogen atoms were thoroughly investigated. The findings demonstrate that the positions of the doping atoms are strongly related to the band gap of doped graphyne. Meanwhile, band structure calculations also clearly reveal that the band gap can be adjusted via BN doping. The ability to regulate the band gap will increase the likelihood of the broad usage of these allotropes in nanoelectronic devices. [ABSTRACT FROM AUTHOR]

In this paper, we study the electrical conductance of a molecular bridge consisting of a graphyne ring with the chemical formula C18H6 connected to two cumulene electrodes using the tightbinding model. We then compare its conductance to a similar system in which the graphyne ring has been replaced by a benzene molecule. To do this, we first obtain the structural characteristics of the studied rings using density functional theory, and then use the method of matching levels, to obtain the tight-binding parameters, i.e., the on-site and hopping energies for the benzene and graphyne rings. Using these parameters, we study the electrical conductance for these two molecules, the benzene and the graphyne rings. We conclude that when these two molecules are in the same position between two cumulene electrodes, they exhibit the same electrical properties. However, in the graphyne ring, a phase transition from metal to semiconductor or vice versa can be created with less energy than in a benzene ring. [ABSTRACT FROM AUTHOR]

In this work, we investigate the hydrogen-storage properties of Zr-decorated γ-graphyne monolayer employing Density Functional Theory (DFT) for green energy storage. We predict that each Zr atom decorated on graphyne sheet (2D) can adsorb up to seven H 2 molecules with an average adsorption energy of −0.44 eV/H 2 , leading to a hydrogen gravimetric density of 7.95 wt%, and desorption temperature of 574 K, particularly suited to fuel-cell applications. Decorated Zr atom strongly attached to graphyne due to charge transfer from Zr to graphyne sheet. Hydrogen molecules adsorb on Zr decorated graphyne due to Kubas type of interactions. The 4.05 eV diffusion energy barrier for the movement of Zr atoms may avoid the metal-metal (Zr–Zr) clustering. The stability of Zr+γ-graphyne is confirmed by performing ab-initio molecular dynamics simulations at room temperature and at estimated average desorption temperature. Hence, our calculations show that Zr functionalized on γ-graphyne could be a promising solid-state hydrogen storage material. [Display omitted] • Zirconium binds on graphyne with energy −3.89eV at the hexagonal position. • Each Zr adsorbs 7H2 molecules leading to 7.95 gravimetric weight % of hydrogen. • Average adsorption energy and desorption temperature are −0.44eV/H2 and 574 K. • Presence of diffusion energy barrier (4.05eV) may avoid metal-metal clustering. • Stability of structure verified from AIMD simulations. [ABSTRACT FROM AUTHOR]

The research on the permeation behavior of small molecules in mixed matrix membranes (MMMs) is an important part of the research of MMMs. Graphyne, a new two‐dimensional carbon material, was used as the filler, and polypyrrole was used as polymer matrix to construct a MMM. In order to clarify the permeation behavior of common small molecules in MMM at room temperature and constant pressure, the adsorption and diffusion properties of H2O, CO2, and O2 in graphyne/polypyrrole MMM were investigated by combining the Giant Canonical Monte Carlo (GCMC) and molecular dynamics (MD). The results show that: (1) the order of adsorption capacity of the three molecules is H2O > CO2 > O2; (2) the diffusion ability of the three molecules is influenced by the doping content of graphyne. Oxygen diffusion and permeation in MMMs are optimal when the graphyne filling level is 15%. The filling of graphyne affects the permeation of gases. It will shed light on application areas such as coating membranes for electronics in special environments, gas separation membranes, and gas sensor membranes. Highlights: A new two‐dimensional carbon nano filler—graphyne was used.A simulation method using a combination of GCMC and MD.The diffusion and permeation behaviors are analyzed from multiple perspectives.The permeation behavior conforms to the solution‐diffusion theory.The graphyne‐filled MMM is conducive to oxygen molecular diffusion. [ABSTRACT FROM AUTHOR]

Graphyne (GY) is a new carbon material with excellent electrical conductivity and low thermal conductivity (TC). The doping of GY into polymers to improve the thermoelectric properties of the material has become a hot research trend. In this study, molecular dynamics (MD) and nonequilibrium MD are used to study the effect of the number of oxidation units of polyaniline (PANI) on TC and heat transfer of PANI and GY/PANI systems. The geometric structure of polymer, interaction energy, and heat transport of all systems are studied and analyzed. It is found that (1) as the number of oxidation units of PANI increases, the interchain and intrachain heat transfers of PANI are decreased thereby decreasing the heat transfer of the PANI chains; (2) the weak interaction energy at the interface hinders the heat flux transfer, and the phonon vibration of GY and PANI mismatch at the interfaces; eventually the above reasons lead to low interface TC; (3) the doping of GY can effectively reduce the TC of the system. This study provides some research ideas and theoretical exploration for the application of polymer doped with GY composites in the field of thermoelectricity. [ABSTRACT FROM AUTHOR]

Owing to the unified and tunable pore size, two-dimensional graphyne membranes show excellent performance in the realm of gas transport and separations. The impacts of environmental conditions on the pore size of a porous membrane are ignored in previous studies. Using molecular modeling techniques, we here probe the accessible pore size of the γ -graphyne membrane under various pressure and temperature conditions. First, by assessing the gas permeation through the two-dimensional γ -graphyne membrane at a constant temperature, the accessible pore size of this membrane is shown to be proportional to the driving force—the pressure difference between the two sides of the porous membrane. Such a driving force dependence is found to be well described by a simple asymptotic model. Then, by determining such pressure dependence at two different temperatures, temperature is found to show a weak influence on the accessible pore size. Finally, by considering the binary mixed gases of various mole fractions, the accessible pore size measured using one of the two species is shown to be dependent on its partial pressure difference. These findings for the accessible pore size, which highlight the tunable pore size by altering the driving force, can be expected to provide a practical strategy to rationalize/refine the pore size of the porous membrane for gas transport and separations, especially for two molecules with similar diameters. [ABSTRACT FROM AUTHOR]

It is shown that it is possible to adapt the quantum graph model of graphene to some types of nonequilateral graphynes considered in the literature; we also discuss the corresponding nanotubes. The proposed models are, in fact, effective models and are obtained through selected boundary conditions and an ad hoc prescription. We analytically recover some results from the literature, in particular, the presence of Dirac cones for α -, β - and (6 , 6 , 12) -graphynes; for γ -graphyne, our model presents a band gap (according to the literature), but only for a range of parameters, with a transition at a certain point with quadratic touch and then the presence of Dirac cones. [ABSTRACT FROM AUTHOR]

The molecular dynamics method is applied to calculate the stiffness constants of five structural configurations of graphyne. The latter is a carbon monolayer in which the atoms are arranged in a special way and characterized by - and -hybritization. It is revealed that the atom arrangement in a graphyne layer has a significant effect on the stiffness constants. It is determined that -graphyne has the highest stiffness constant (1091 GPa) and that -graphyne has the smallest one (258 GPa). As shown in the study, - and -graphyne are highly anisotropic structures. [ABSTRACT FROM AUTHOR]

In this paper, we investigated the hydrogen storage capacity of OLi 3 decorated graphyne and graphdiyne using density functional theory calculation. The optimization results showed that the OLi 3 superalkalis were anchored strongly on the graphyne and graphdiyne with the adsorption energy of −3.82 and −4.04 eV, respectively. The binding energy between OLi 3 and carbon nanosheet is much higher than that between two OLi 3 superalkalis, indicating their uniform dispersion over the carbon material surface without any aggregation. The thermal stability has also been verified by ab inito molecular dynamics simulation. Decorating with OLi 3 can effectively improve the hydrogen storage capacity of carbon monolayers. The hydrogen storage capacities of 4OLi 3 /GY and 8OLi 3 /GDY complexes are 7.23 and 8.87 w. t. %, with the average hydrogen adsorption energy of −0.252 and −0.218 eV per H 2. The binding energy between Li and its neighboring H 2 is contributed by the electron transfer and some orbital hybridization. The results suggest the complexes with reversible hydrogen storage properties at ambient temperature, indicating their potential use as promising hydrogen storage candidates. • Large binding energy and electrostatic repulsion hinder the clustering of OLi 3. • The decoration with OLi 3 significantly increase the HSC of graphyne and graphdiyne. • The hydrogen adsorption energy of 4OLi 3 /GY and 8OLi 3 /GDY are −0.252 and −0.218 eV. • The T D ensure 4OLi 3 /GY to be hydrogen storage medium under moderate temperature. [ABSTRACT FROM AUTHOR]

Recently, γ−graphyne has been recognized as a two-dimensional high-order topological insulator with typical corner states. In this work, we examine the condition for the existence of corner states in a hexagonal quantum dot made of γ−graphyne (GYQD). Based on a single-orbital tight-binding model, we find that corner states appear only when there are partially-bonding carbon atoms located at the corners. This indicates a potential instability of corner states. As the size of GYQDs increases, mid-gap states in the energy spectrum are either prohibited or exhibited as corner-only or edge-only states. Additionally, we find that the light absorption of GYQDs has a relatively weak polarization anisotropy. The presence of corner states leads to the emergence of sub-gap absorption and enhancement of above-gap absorption.

In this study, graphdiyne was prepared using a γ-irradiated N-doping photogram to transform two-dimensional graphdiyne into a one-dimensional tubular structure for use as substrate-supported iron nanoparticles for cathodic redox reaction (ORR) in fuel cells. Methods such as scanning electron microscopy, X-ray diffraction, Raman spectroscopy, and isothermal nitrogen adsorption and other characterization methods were used to characterize and analyze the surface morphology, element composition, crystalline structure, and defect degree of the prepared composites. In the alkaline solution, the prepared catalyst was characterized by ORR performance, four-electron selectivity, kinetics and stability via cyclic voltammetry test, linear sweep voltammetry test and electrochemical AC impedance spectroscopy test. The results showed that after γ-ray irradiation, the nitrogen-doped graphite monoalkyne-loaded iron nanoparticle (NGY-Fe) catalyst had a larger specific surface area (411.3 m2/g) and a multilevel pore structure, which was conducive to the exposure of the active center. Moreover, the O2 permeation barrier was decreased, and the ORR activity of the NGY-Fe was significantly improved, especially in terms of the stability and methanol resistance, which were far superior to those of the commercially available commercial Pt/C catalysts.

There are increasing concerns about the environmental impact of rising atmospheric carbon monoxide concentrations, thus it is necessary to develop new catalysts for efficient CO oxidation. Based on first-principles calculations, the potential of γ-graphyne (GY) as substrate for metals in the 4th and 5th periods under single-atom and dual-atoms concentration modes has been systematically investigated. It was found that single-atom Co, Ir, Rh, and Ru could effectively oxidate CO molecules, especially for single Rh. Furthermore, proper atoms concentration could boost the CO oxidation activity by supplying more reaction centers, such as Rh2/GY. It was determined that two Rh atoms in Rh2/GY act different roles in the catalytic reaction: one structural and another functional. Screening tests suggest that substituting the structural Rh atom in the center of acetylenic ring by Co or Cu atom is a possible way to maintain the reaction performance while reducing the noble metal cost. This systemic investigation will help in understanding the fundamental reaction mechanisms on GY-based substrates. We emphasize that properly exposed frontier orbital of functional metal atom is crucial in adsorption configuration as well as entire catalytic performance. This study constructs a workflow and provides valuable information for rational design of CO oxidation catalysts. [ABSTRACT FROM AUTHOR]

The present study focuses on the thermo-mechanical modelling of pristine graphyne, BN-substituted graphyne, and graphyne-like BN utilizing molecular dynamics (MD) simulation. Considering the results of uniaxial tensile MD simulations, respective structures indicate outstanding mechanical properties. In particular, the pristine graphyne (note that it only consists of C–C atomic bond type) has superior mechanical properties compared to others. Besides, graphyne-like BN demonstrates the lowest mechanical properties due to consisting of only B–N bonds. MD simulations are conducted for different temperatures and strain rates varying between 1 K–1200 K and 107 s−1–109 s−1, respectively. With increasing temperature, a gradual decrease in mechanical properties is observed due to the high temperature's weakening effect. Mechanical properties of graphyne-like BN are affected by the change in temperature more than other structures. Furthermore, findings of MD simulation show that the mechanical properties of aforementioned structures have an increasing trend with increasing strain rates. Similar to mechanical properties, pristine graphyne, BN-substituted graphyne, and graphyne-like BN have superior thermal conductivity (TC) properties. Non-equilibrium MD simulation results illustrate that the pristine graphyne containing C–C bonds exhibits the largest TC value. In contrary, the graphyne-like BN comes up with a low TC value. Temperature increase (from 200 to 900 K) affects TC values negatively owing to increase in phonon–phonon scattering. Finally, the results of this study make aforementioned structures a splendid competitor for thermo-mechanical practice of 2D-based structures. [ABSTRACT FROM AUTHOR]

[Display omitted] • This study used DFT and analyzed mustard gas adsorption onto graphynes nanoclusters. • Mustard gas molecules could not be strongly adsorbed onto bare graphyne. • BN-doped graphyne can serve as an efficient electronic sensor of mustard gas. Density functional theory (DFT) calculations are used to thoroughly examine the reactivity and electronic sensitivity of pristine and BN-doped graphyne (BNG) toward nitrogen mustard (NM). Graphyne's electrical conductivity is unaffected by the weak adsorption of NM, which occurs via the Cl atom on the material with an adsorption energy of roughly −3.1 kcal.mol−1. In addition to decreasing graphyne's reactivity and work function, substituting isoelectronic B N linkages for C C linkages enhances the HOMO-LUMO energy gap (Eg). BNG's electrical conductivity increases when Eg drops from 2.99 to 1.82 eV due to the adsorption of NM. Additionally, a significant change in BNG's work function results in a variation in the field electron emission current. Lastly, it is anticipated that the desorption of NM from the BNG surface will take a brief recovery time of roughly 0.05 s at room temperature. It has also been demonstrated that NM concentration affects changes in electrical conductivity. The findings also suggest that BNG could be a promising NM sensor. [ABSTRACT FROM AUTHOR]

After the synthesis of graphene (Gr), the other two-dimensional (2D) allotropes of carbon based materials have been predicted theoretically or synthesized by experimentally. Two of these nanomaterials are graphyne (Gy) and graphdiyne (Gdy) which are close relatives of Gr and can be synthesized in bulk. While carbon atoms in Gr bonds with s p 2 bonds, Gy and Gdy comprise s p and s p 2 hybridized carbon atoms with high degrees of π conjugation that features uniformly distributed pores. So, these intrinsic nanopores add distinction to Gy and Gdy with respect to the Gr especially for energy storage applications. Nowadays, the researchers are studying to improve the storage capacity of Lithium-ion batteries (LIBs). However, Lithium–Sulfur (Li–S) batteries can store approximately five times more energy in terms of energy density compared to LIBs. In this study, we have systematically investigated the lithium polysulfides (Li x S y ; 1 ≤ x ≤ 2 , 1 ≤ y ≤ 8) adsorbed on Gr, Gy and Gdy monolayers by means of density functional theory (DFT) calculations. Our results reveal that, the presence of s p bonds and the size of nanopores in the structure extremely affect the adsorption energy of small sized Li x S y clusters. However, the adsorption energies obtained with increasing the size of Li x S y clusters are almost similar in Gr, Gy and Gdy monolayers. The diffusion barrier energy values obtained for Li x S y clusters indicate that the migration of clusters on Gr may be easy but it is hard on Gdy and especially on Gy due to the pore networks in the structures acting as traps to anchor the Li x S y clusters. In addition, we have investigated the double adsorption of Li x S y clusters on Gr, Gy and Gdy structures to search the shuttle effect. It can be reported that Li x S y clusters do not bind each others and do not create long polysulfide chains, which is not requested. [Display omitted] • The s p bonds and pore size in Gy and Gdy are effective on the diffusion of Li–S clusters. • The E b a r values of Li–S clusters on Gr, Gy and Gdy are close to commercial electrode materials. • None of the Li–S clusters create long polysulfide chains on the Gy and Gdy. [ABSTRACT FROM AUTHOR]

Graphyne (two-dimensional one-atom-thick carbon allotrope) a promising semiconductor distinct by the number of acetylenic bonds. The study of mechanical properties is of key importance for electronics, composite fabrication, and fundamental understanding of the mechanical behavior of 2D structures. Molecular dynamics and analytical calculations were used to obtain the elastic constants (stiffness and compliance constants, Young's and shear modulus, Poisson's ratio) for five graphynes. For the first time, the direct link between stiffness and compliance constants for 2D materials were presented. Among hexagonal graphynes, γ 1 has the largest Young's modulus (154 N/m). The deformation is attributed to the competition between the rotation and elongation of bonds in graphyne under loading. An analysis of stationary and extreme values of Young's and shear modulus, Poisson's ratio was carried out for the first time based on the search for the extremum of a function of one variable. A strong mechanical anisotropy was observed for orthorhombic graphynes (β 3 and γ 2). Orthorhombic graphynes possess extremely large in-plane Poisson's ratio. Explanation of how elastic constants depend on structure density and atomic arrangement was given. The obtained results open new opportunities for the development of new nanomechanical devices based on such 2D materials. • Graphyne elastic properties are investigated by molecular dynamics and analytically. • Relationship between stiffness and compliance constants for 2D materials are presented. • Orientation dependencies of elastic constants is presented for graphyne. [Display omitted] [ABSTRACT FROM AUTHOR]

Owing to the unified and tunable pore size, two-dimensional graphyne membranes show excellent performance in the realm of gas transport and separations. The impacts of environmental conditions on the pore size of a porous membrane are ignored in previous studies. Using molecular modeling techniques, we here probe the accessible pore size of the γ-graphyne membrane under various pressure and temperature conditions. First, by assessing the gas permeation through the two-dimensional γ-graphyne membrane at a constant temperature, the accessible pore size of this membrane is shown to be proportional to the driving force—the pressure difference between the two sides of the porous membrane. Such a driving force dependence is found to be well described by a simple asymptotic model. Then, by determining such pressure dependence at two different temperatures, temperature is found to show a weak influence on the accessible pore size. Finally, by considering the binary mixed gases of various mole fractions, the accessible pore size measured using one of the two species is shown to be dependent on its partial pressure difference. These findings for the accessible pore size, which highlight the tunable pore size by altering the driving force, can be expected to provide a practical strategy to rationalize/refine the pore size of the porous membrane for gas transport and separations, especially for two molecules with similar diameters.

The search for new materials is constantly ongoing. Recently, a two-dimensional carbon allotrope , γ-graphyne, has been synthesized with a unified crystalline structure . Because of its low LUMO and excellent electron mobility, it appears to be a promising electron acceptor for photovoltaic applications. Here we report an analysis of the electronic properties of model van der Waals complexes of γ-graphyne with several partners of different electronic nature. We show that photoinduced electron transfer from electron-donating partners to γ-graphyne is favorable and occurs on nano to picosecond time scale. In contrast, electron transfer from γ-graphyne to strong electron acceptors is unlikely. Our results open perspectives for the future application of γ-graphyne in photovoltaic devices.

In this theoretical work, density functional theory calculations show the effect of small cobalt clusters (Con, n = 1–5) adsorbed on pristine γ‐graphyne (γ‐GY), and modify N‐doped γ‐GY monolayers (GYNs‐def). Different geometrical configurations are assessed with the adsorption energy, charge transfer, and density of states. The system with vacancy defects shows a large adsorption energy (19.96 eV) for the Co5 cluster. This behavior may be associated to the overlapping of the electronic state contributions between cobalt and carbon atoms in the valence states. This indicates that the Co5 cluster could be deposited on N‐doped γ‐GY monolayers (Con@GYNs‐def). The lowest‐energy systems are evaluated to estimate the strength of the interaction with hydrogen molecules (xH2, where x = 1–5). According to the adsorption energy values, the modified γ‐GY monolayers are allowed to be a suitable support material to capture H2 molecules via the small Con clusters. The hydrogen retention capacity for the supported cobalt atoms corresponding to the lowest‐energy configurations and larger systems are evaluated by using molecular dynamics simulations with the Born–Oppenheimer approximation. The role played by defects in the GYNs‐def monolayers is important, since the Con clusters remain attached to the vacancy with the absence of surface diffusion. This study may represent a guide to tailor novel nanostructures based on small cobalt clusters supported on graphyne monolayers modified to be applied in H2 adsorption. [ABSTRACT FROM AUTHOR]

Stable configurations of transition metal atom anchored graphyne（M-gra） systems and their sensitivities and selectivities for various small gas molecules are studied using the first-principles methods based on density functional theory. It is found that the adsorption of metal atoms at H2 site of the pore structure has high stability. Different types of metal atoms can effectively control the electronic property and magnetic moments of graphyne system. According to the adsorption energy values of gas molecules, the M-gra substrates exhibit high sensitivity for adsorbed O and OH, and the stability of individual NO, NO2 or O2 is more than that of CO molecule. In addition, the small molecules adsorbed M-gra systems exhibit the metal, semi-metal and semiconducting properties, which have potential applications in the field of electronics and gas sensors devices. [ABSTRACT FROM AUTHOR]

The ability to remove carbon dioxide from gaseous mixtures is a necessary step toward the reduction of greenhouse gas emissions. As a contribution to this field of research, we performed a molecular dynamics study assessing the separation and adsorption properties of multi-layered graphtriyne membranes on gaseous mixtures of CO2, N2, and H2O. These mixtures closely resemble post-combustion gaseous products and are, therefore, suitable prototypes with which to model possible technological applications in the field of CO2 removal methodologies. The molecular dynamics simulations rely on a fairly accurate description of involved force fields, providing reliable predictions of selectivity and adsorption coefficients. The characterization of the interplay between molecules and membrane structure also permitted us to elucidate the adsorption and crossing processes at an atomistic level of detail. The work is intended as a continuation and a strong enhancement of the modeling research and characterization of such materials as molecular sieves for CO2 storage and removal. [ABSTRACT FROM AUTHOR]

The electronic sensitivity of pure, P-doped and Ga-doped graphyne to arsine was studied by density functional theory calculations. As AsH3 approaches the graphyne, its adsorption releases 3.6 to 5.2 kcal mol–1 of energy, indicating weak adsorption. Also, the electronic properties of the sheet do not change significantly. Unlike P-doping, Ga-doping improves the performance of the graphyne and makes it more reactive and sensitive to AsH3. According to the calculations, the AsH3 adsorption reduces the HOMO/LUMO gap (Eg) of the Ga-doped graphyne from 2.27 to 1.58 eV (approximately –30.40%), which concludes that the electrical conductivity of the nanosheet has increased. Thus, the Ga-doped sheet can generate electrical signals when the AsH3 molecules approach. But AsH3 could not significantly alter the electronic properties of P-doped graphyne. [ABSTRACT FROM AUTHOR]

NanoTube Construct is a web tool for the digital construction of nanotubes based on real and hypothetical single-layer materials including carbon-based materials such as graphene, graphane, graphyne polymorphs, graphidiyene and non-carbon materials such as silicene, germanene, boron nitride, hexagonal bilayer silica, haeckelite silica, molybdene disulfide and tungsten disulfide. Contrary to other available tools, NanoTube Construct has the following features: a) it is not limited to zero thickness materials with specific symmetry, b) it applies energy minimisation to the geometrically constructed Nanotubes to generate realistic ones, c) it derives atomistic descriptors (e.g., the average potential energy per atom, the average coordination number, etc.), d) it provides the primitive unit cell of the constructed Nanotube which corresponds to the selected rolling vector (i.e., the direction in which the starting nanosheet is rolled to form a tube), e) it calculates whether the Nanotube or its corresponding nanosheet is more energetically stable and f) it allows negative chirality indexes. Application of NanoTube Construct for the construction of energy minimised graphane and molybdenum disulfide nanotubes are presented, showcasing the tool's capability. NanoTube Construct is freely accessible through the Enalos Cloud Platform (https://enaloscloud.novamechanics.com/diagonal/nanotube/)., Competing Interests: PK, DZ, NS, AT and AA are employed by NovaMechanics, a cheminformatics and materials informatics company., (© 2024 The Authors.)

It is shown that it is possible to adapt the quantum graph model of graphene to some types of nonequilateral graphynes considered in the literature; we also discuss the corresponding nanotubes. The proposed models are, in fact, effective models and are obtained through selected boundary conditions and an ad hoc prescription. We analytically recover some results from the literature, in particular, the presence of Dirac cones for α-, β- and (6,6,12)-graphynes; for γ-graphyne, our model presents a band gap (according to the literature), but only for a range of parameters, with a transition at a certain point with quadratic touch and then the presence of Dirac cones.

As a new two-dimensional carbon material, grapheyne has π conjugated units, SP² and SP hybrid carbon atoms and adjustable pore structure. It has stable structure, good conductivity and strong plasticity. Its structure can be adjusted by hybridization or modification. It has a good application prospect in the field of electrochemistry. This paper briefly introduced different types of graphyne and their structures, such as α-graphyne, β-graphyne, γ-graphyne and 6,6,12-graphyne, as well as graphdiyne. The synthesis strategies of graphyne and its derivatives are described, including wet and dry methods. There are in-situ synthesis methods of different types of graphyne and graphdiyne, and different structures are obtained through different synthesis or growth methods, such as nano films, nano sheets and nano chains. It also includes the preparation strategy of graphyne derivatives, which adjusts the structure by heteroatom doping or metal atom modification, such as nitrogen atom doping, platinum atom modification and so on. The advanced research results of graphyne and its derivatives in the field of energy are reviewed, including the research results of graphyne and its derivatives in lithium-ion batteries, hydrogen oxygen fuel cells, sodium ion batteries, supercapacitor and other electrochemical energy storage devices and materials. As the anode of lithium-ion battery, the coulomb efficiency and cycle performance of the battery are improved, and the stability of the battery is enhanced. It has good catalytic performance for oxygen reduction reaction and has the prospect of being used as a catalyst for hydrogen oxygen fuel cell. It also has good storage performance for sodium, calcium and magnesium, and has good potential in application with sodium ion batteries and multivalent ion batteries. It shows good cycle performance and specific capacity in supercapacitor. In addition, it also has good theoretical capacity in hydrogen storage. It has a good application prospect in a variety of electrochemical energy storage devices. Comprehensive analysis shows that graphyne, as a new allotrope of carbon, has good performance and optimization potential in structure and electrochemical properties. It has a good development prospect in electrochemical energy storage devices in the future. [ABSTRACT FROM AUTHOR]

Graphyne, a promising carbon candidate for energy storage and conversion, has been prepared successfully via a mechanochemical route. However, inevitable graphitic carbon species generate concomitantly. In this work, we synthesize rich pyridonic-/pyridinic-nitrogen doped graphyne (NGY) employing calcium carbide and asymmetric pentachloropyridine (PCP) as precursors and find that introducing symmetric hexabromobenzene (HBB) can suppress the formation of graphitic carbon impurities. The symmetry of organic precursors is a key to the yield of NGY during the mechanochemical process, so a competitive formation mechanism between NGY and graphitic carbon species is proposed according to experimental results and theoretical calculation. Compared with the samples obtained from single asymmetric PCP or symmetric HBB, an optimized NGY (1:1 molar ratio of PCP/HBB) increases the Li-storage capacity by 11% and 52% respectively, owing to abundant Li+ adsorption and high structural stability. This work highlights organic precursor symmetry for undergoing mechanochemical cross-coupling and brings new insights to in-situ constructing heteroatom-doped alkynyl carbon frameworks. We have demonstrated mechanochemical synthesizing nitrogen-doped graphyne, affording competitive lithium storage performance, and found that the feeding ratio of symmetric organic precursors is a key for suppressing inevitable graphitic carbon species. [Display omitted] [ABSTRACT FROM AUTHOR]

Graphyne is a new carbon material with excellent electrical conductivity. It is a research hotspot that using graphyne as polymer filler to enhance the thermal conductivity of composite materials. In this study, the structure, electronic properties, and thermal conductivity of graphyne (GY), polypyrrole (PPy), and graphyne/polypyrrole (GY/PPy) composite materials are studied using density functional theory (DFT), molecular dynamics simulation (MD), and nonequilibrium molecular dynamics simulation (NEMD). It is found that graphyne with approximate aspect ratio has better electronic conductivity. The thermal conductivity of GY/PPy composites with different mass fractions is studied by NEMD. The results show that when 7‐GY‐2 is 20%, the thermal conductivity of GY/PPy composite is about 90% higher than that of pure PPy. In order to further study the interaction of GY/PPy, the electronic properties of the local configuration (GY‐PPy) of the composite are studied. The results show that the strong interaction between graphyne and polypyrrole improves the conductivity of GY‐PPy. This study provides some research ideas and theoretical exploration for improving the electrical conductivity and thermal conductivity of polymer doped with graphyne. [ABSTRACT FROM AUTHOR]

Sodium-ion batteries (SIBs) are promising candidates for the replacement of lithium-ion batteries (LIBs) because of sodium's abundant reserves and the lower cost of sodium compared to lithium. This is a topic of interest for developing novel anodes with high storage capacity. Owing to their low cost, high stability, and conductivity, carbon-based materials have been studied extensively. However, sp2-C based carbon materials have low-rate capacities. Intensive density functional theory calculations have been implemented to explore the applicability of α, β, and γ graphyne nanotubes (αGyNTs, βGyNTs, and γGyNTs, respectively) as SIB anodes. Results suggest that (3, 0)-αGyNT, (2, 2)-βGyNT, and (4, 0)-γGyNT have, respectively, maximum Na storage capacities of 1535, 1302, and 1001 mAh/g, which exceeds the largest reported value of carbon materials (N-doped graphene foams with 852.6 mAh/g capacity). It was determined that αGyNTs have the largest storage capacity of the three types because they possess the largest specific surface area. Moreover, the larger pores of αGyNTs and βGyNTs allow easier diffusion and penetration of Na atoms compared to those of γGyNTs, which could result in better rate capacity. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hydration influences the structure of the electric double layer, affecting ion density on electrode surfaces. • Hydration optimizes gravimetric energy density. • Positive ions are more concentrated on graphene electrodes compared to graphyne. This study systematically analyzes the structural properties of the ionic liquids 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF 4 ]) and choline-glycine ([cho][gly]) to evaluate hydration effects on their electrical properties in supercapacitors with graphene or graphyne electrodes. The research examines how hydration impacts the electric window, total capacitance and gravimetric energy density of the devices. The goal is to enhance energy storage performance through innovative materials, focusing on sustainable, eco-friendly technologies. Results show that hydration influences the structure of the Electric Double Layer (EDL), with water molecules affecting ion mass density on the surface of the electrodes. Positive ion concentration is higher in graphene electrodes compared to graphyne. The study projects gravimetric energy density and energy efficiency based on potential difference and hydration level, highlighting the critical role of hydration in optimizing supercapacitor electrical properties and industrial application opportunities. [ABSTRACT FROM AUTHOR]

The different phases of α-, β-, and γ-graphyne, which are new types of two-dimensional carbon allotropes, hold promise as potential candidates for designing substrate discs in piezoelectric nanogenerators. Accurate modeling of the bending rigidity and stretching properties as well as resonance frequencies of these materials is crucial for engineering applications like nano-resonator and nanogenerator systems. This step is imperative in designing and advancing future applications involving these structures. This study aims to create a hybrid atomistic-continuum model for modeling graphyne monolayers used as substrate discs in nanogenerators. The model integrates the benefits of both atomistic and continuum approaches. Based on the results, α-graphyne is the least mechanically stable, while γ-graphyne is the most stable. However, in terms of vibration frequency, α-graphyne has the highest frequency while γ-graphyne has the lowest. Therefore, β-graphyne, with moderate stability and resonance frequency, is recommended as the ideal choice for the substrate disc in piezoelectric nanogenerators. It can function within the Q-F frequency range (30–140 GHz) and induce deformation in the piezoelectric shim as well as generation voltage. [Display omitted] • Offering nanogenerators to harvest vibration energy from the millimeter-wave. • Introducing graphyne (α, β, γ) circular sheets as substrate disc in nanogenerators. • The sequence of mechanical stability is α- < β- < γ-graphyne. • The trend of the fundamental natural frequency is (α- > β- > γ- graphyne). • Within the frequency range of 30–140 GHz, β-graphyne recommend as substrate discs. [ABSTRACT FROM AUTHOR]

This study delves into the geometrical structure, electronic characteristics, and optical properties of hydrogen (H) and fluorine (F) substituted graphyne (GY) and graphdiyne (GDY) sheets using density functional theory (DFT). The investigated sheets are denoted as R-GY and R-GDY, where R represents either H or F. Our results reveal the energetic stability of these sheets through cohesive energy calculations and confirm their thermal stability via ab-initio molecular dynamics (AIMD) simulations. It is found that R-GY and R-GDY sheets are semiconductors. The optical characteristics of H-substituted sheets closely resemble those of F-substituted ones. The findings showcase the strong light-absorbing capabilities of R-GY and R-GDY sheets in the visible and ultraviolet regions, making them favorable materials for applications in photovoltaic systems and ultraviolet absorbers. The reflection and transmission coefficients indicate the high transparency of the sheets for light. Our findings could enhance the understanding of the electronic and optical properties of R-GY and R-GDY, potentially inspiring researchers to develop optoelectronic devices utilizing these materials. [ABSTRACT FROM AUTHOR]

This review aims to offer a comprehensive and critical understanding of mechano-chemical synthesis of γ-graphyne (γ-GY). Through the discussion of reaction mechanism and synthetic limits, it is verified that the product indeed contains the compound of γ-GY, but the defects such as graphitized carbon introduced in the process are inevitable. [Display omitted] • A comprehensive insight into the mechanochemical synthesis of full-carbon graphyne material including its advances and limits. • The key synthetic strategies for graphyne carbon and corresponding characterization results are summarized and discussed. • Previous origin (environmentally mechanochemical dehalogenation) and subsequent developments (synthesis for other alkynyl cross-linked carbon derivatives) for mechanosynthesic graphyne are introduced in detail. • Fabrication mechanism of γ-graphyne via the mechanochemcial synthesis is specifically elucidated and carbonaceous impurities are inevitably induced during the process. • Future development suggestions for mechanochemical preparation of graphyne material are proposed. Graphyne, a novel regularly sp-/sp2-hybridized carbon allotrope, has attracted significant interest in synthetic chemistry and various applications. As a promising approach for material synthesis, mechanochemistry has first been successfully applied to fabricate γ-graphyne (γ-GY) which exhibits highest structural stability among graphyne family and possesses fascinating properties like a direct bandgap and unique nanoporosity. The γ-GY skeleton forms via an alkyne nucleophilic cross-coupling reaction induced by intense mechanical energy using hexahalobenzene and calcium carbide as precursors. This mechanochemical strategy is simple, high-yielding, scalable, and commercially viable. This review aims to offer a comprehensive and critical understanding of mechanochemical synthesis of γ-GY. Firstly, the basic concept, physicochemical properties and potential applications of graphyne, especially γ-GY, are introduced. Subsequently, the review summarizes several state-of-the-art synthetic strategies for γ-GY and corresponding representative characterizations. Furthermore, the feasibility of mechanosynthesis for γ-GY is elucidated through the discussion of its origin which involves mechanochemical dehalogenation, and its subsequent development for the synthesis of alkynyl cross-linked carbon derivatives. The reaction mechanism, and controversial factors (including solvent issue, side reaction, and carbonaceous impurities) of the mechanochemical route are adequately outlined and analyzed. Evidence confirms the existence of γ-GY in the as-prepared sample and inevitable generation of by-products such as carbonaceous impurities. Finally, the challenges and future research directions of mechanochemical synthesizing high-quality γ-GY and derivatives (analogues) are proposed. [ABSTRACT FROM AUTHOR]

[Display omitted] • Graphyne is explored as a carrier for Purinethol drug. • Graphyne has significant therapeutic potential as a drug carrier. • The DFT calculation was used to study the interaction of the drug Purinethol with graphdiyne. • The adhesion energy of the Purinethol drug on the graphydine surface was calculated at about −1.87 eV. Within this piece of research, DFT calculations were undertaken in order to investigate the drug-loading performance of graphyne for Purinethol. In order to evaluate the possibility of using graphyne as a carrier, the energetic, geometrical and optimized attributes of graphyne, Purinethol, and the complex of graphyne and Purinethol were investigated. We investigated three sites, namely a, b and c, in the structures of Purinethol for its interaction with graphyne. The most suitable interaction was the one in which sulfur and nitrogen atoms were involved. Purinethol had an interaction with graphyne with the adhesion-energy of −1.87 eV in the gaseous phase. The non-covalent interaction analysis was performed to explore the interaction of graphyne with Purinethol. Based on the analysis results, the interaction forces of the complex of graphyne and Purinethol were weak. The HOMO-LUMO analysis and charge-decomposition analysis were performed to describe the charge transported from Purinethol to graphyne during the formation of graphyne and Purinethol. The results demonstrated the possibility of using graphyne as a suitable carrier for Purinethol. The theoretical results obtained within this work can inspire researchers to find novel 2D nanomaterials for drug delivery purposes. [ABSTRACT FROM AUTHOR]

Elemental engineering has been employed to adjust molecular framework and electronic configuration of γ-graphyne for rapid lithium storage. Here, we construct a quasi-pyridinic nitrogen/sulfur co-doped γ-graphyne (N/S-GY) via a mechanochemical strategy and reveal its lithium storage behavior by quantitative kinetics analysis and theoretical calculations. The internal pyridinic-N atoms create rhombic channels for Li+ passing through, while sulfur dopants anchored with alkynyl groups induce electron cloud rearrangement to facilitate intralayer Li+ diffuse between C 12 -triangular channels and interlayer transfer through open rhombic channels. As a result, the as-prepared N/S-GY exhibits a high reversible capacity of 1003 mAh g−1 at 50 mA g−1 after 150 cycles, with Li+ diffusion coefficient up to 2.6 × 10−12 cm2 s−1, both of which are larger than that of N-doped γ-graphyne. This work highlights synergistic effect of sulfur and nitrogen co-doping in alkynyl carbon and inspires bottom-up heteroatom modification in framework design. [Display omitted] • Sulfur and nitrogen co-doped γ-graphyne has been prepared through a mechanochemical route. • The N/S-GY anode displays high lithium-ion capacity with 1003 mAh g−1 at 50 mA g−1 after 150 cycles. • The N/S-GY anode exhibits lithium diffusion efficiency with 2.6 × 10−12 cm2 s−1. [ABSTRACT FROM AUTHOR]