In-situ sonochemical formation of N-graphyne modulated porous g-C3N4 for boosted photocatalysis degradation of pollutants and nitrogen fixation.

Herein, Nitrogen-doped graphyne/porous g-C3N4 composites are firstly in-situ synthesized via the ultrasound vibration of CaC2, triazine, and porous g-C3N4 in absolute ethanol. A variety of characterizations are performed to investigate the morphology, microstructure, composition, and electrical/optical features of the obtained composites, such as transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectra, X-ray photoelectron spectroscopy, and so forth. It is found that N-doped graphyne with flexible folds lamellar structure is intimately attached to flake g-C3N4 in the as-prepared composites. An enlargement of 1.68 and 1.44 folds for the photocatalytic degradation of levofloxacin, rhodamine B, Methylene blue, and Tetracycline is realized by N-doped graphyne/g-C3N4 in comparison with that of pristine g-C3N4, respectively. In addition, the highest NH3 production rate attains 1.71 mmol⋅gcat-1⋅h-1 for N-doped graphyne/g-C3N4, which is 5.89 times larger than that of g-C3N4 (0.29 mmol⋅gcat-1⋅h-1). The improved mechanism of photocatalysis including higher photo-response and carrier separation rate is verified by transient photo-current, transient photo-potential, Mott-Schottky plots, Tafel plots, electrochemical impedance spectroscopy, turn-over frequency, photoluminescence spectra, and UV-vis diffuse absorption spectra, etc. Overall, the current study shows that N-doped graphyne synthesized from CaC2 and triazine is a useful decoration to modulate the photocatalytic features of g-C3N4, which can also be widely extended for in-situ modification of other photocatalysts.

Enhanced Elastocaloric Effects in γ-Graphyne.

The global emphasis on sustainable technologies has become a paramount concern for nations worldwide. Specifically, numerous sustainable methods are being explored as promising alternatives to the well-established vapor-compression technologies in cooling and heating devices. One such avenue gaining traction within the scientific community is the elastocaloric (eC) effect. This phenomenon holds promise for efficient cooling and heating processes without causing environmental harm. Studies carried out at the nanoscale have demonstrated the efficiency of the eC effect, proving to be comparable to that of state-of-the-art macroscopic systems. In this study, we used classical molecular dynamics simulations to investigate the elastocaloric effect for the recently synthesized γ-graphyne. Our analysis goes beyond obtaining changes in eC temperature and the coefficient of performance (COP) for two species of γ-graphyne nanoribbons (armchair and zigzag). We also explore their dependence on various conditions, including whether they are deposited on a substrate or prestrained. Our findings reveal a substantial enhancement in the elastocaloric effect for γ-graphyne nanoribbons when subjected to prestrain, amplifying it by at least 1 order of magnitude. Under certain conditions, the changes in the eC temperature and the COP of the structures reach expressive values as high as 224 K and 14, respectively. We discuss the implications of these results by examining the shape and behavior of the carbon-carbon bond lengths within the structures.

Effect of Strain Rate, Temperature, Vacancy, and Microcracks on Mechanical Properties of 8-16-4 Graphyne.

The 8-16-4 graphyne, a recently identified two-dimensional carbon allotrope, exhibits distinctive mechanical and electrical properties, making it a candidate material for flexible electronic applications. This study endeavors to enhance our comprehension of the fracture behavior and mechanical properties of 8-16-4 graphyne. The mechanical properties of 8-16-4 graphyne were evaluated through molecular dynamics simulations, examining the impact of boundary conditions, temperature, and strain rate, as well as the coupled interactions between temperature, vacancy defects, and microcracks. The findings reveal that 8-16-4 graphyne undergoes fracture via the cleavage of ethylene bonds at a critical strain value of approximately 0.29. Variations in boundary conditions and strain rate influence the fidelity of tensile simulation outcomes. Temperature, vacancy concentration, and the presence of microcracks markedly affect the mechanical properties of 8-16-4 graphyne. In contrast to other carbon allotropes, 8-16-4 graphyne exhibits a diminished sensitivity to vacancy defects in its mechanical performance. However, carbon vacancies at particular sites are more prone to initiating cracks. Furthermore, pre-existing microcracks within the material can potentially alter the fracture mode.

Coordination Environment Engineering to Regulate the Adsorption Strength of Intermediates in Single Atom Catalysts for High-performance CO2 Reaction Reduction.

The modulation of the coordination environment of single atom catalysts (SACs) plays a vital role in promoting CO2 reduction reaction (CO2RR). Herein, N or B doped Fe-embedded graphyne (Fe-GY), Fe-nXGYm (n = 1, 2, 3; X = N, B; m = 1, 2, 3), are employed as probes to reveal the effect of the coordination environment engineering on CO2RR performance via heteroatom doping in SACs. The results show that the doping position and number of N or B in Fe-GY significantly affects catalyst activity and CO2RR product selectivity. In comparison, Fe-1NGY exhibits high-performance CO2RR to CH4 with a low limiting potential of -0.17 V, and Fe-2NGY3 is demonstrated as an excellent CO2RR electrocatalyst for producing HCOOH with a low limiting potential of -0.16 V. With applied potential, Fe-GY, Fe-1NGY, and Fe-2NGY3 exhibit significant advantages in CO2RR to CH4 while hydrogen evolution reaction is inhibited. The intrinsic essence analysis illustrates that heteroatom doping modulates the electronic structure of active sites and regulates the adsorption strength of the intermediates, thereby rendering a favorable coordination environment for CO2RR. This work highlights Fe-nXGYm as outstanding SACs for CO2RR, and provides an in-depth insight into the intrinsic essence of the promotion effect from heteroatom doping.

Topological electronic states in holey graphyne.

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 withC2symmetry 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 emergentg-like andh-like orbitals gives rise to a nontrivial topology characterized byZ2invariant 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.

Exploring the Potential of Chemically Modified Graphyne Nanodots as an Efficient Adsorbent and Sensitive Detector of Environmental Contaminants: A First Principles Study.

In this study, we investigated the reactivity of γ-graphyne (Gp) and its derivatives, Gp-CH3, Gp-COOH, Gp-CN, Gp-NO2, and Gp-SOH, for the removal of toxic heavy metal ions (Hg+ 2, Pb+ 2, and Cd+ 2) from wastewater. From the analysis of the optimized structures, it was observed that all the compounds exhibited planar geometry. The dihedral angles (C9-C2-C1-C6 and C9-C2-C1-C6) were approximately 180.00°, indicating planarity in all molecular arrangements. To understand the electronic properties of the compounds, the HOMO (EH) and LUMO (EL) energies were calculated, and their energy gaps (Eg) were determined. The EH and EL values ranged between - 6.502 and - 8.192 eV and - 1.864 and - 3.773 eV, respectively, for all the compounds. Comparing the EH values, Gp-NO2 exhibited the most stable HOMO, while Gp-CH3 had the least stable structure. In terms of EL values, Gp-NO2 had the most stable LUMO, while Gp-CH3 was the least stable. The Eg values followed the order: Gp-NO2 < Gp-COOH < Gp-CN < Gp-SOH < Gp-CH3 < Gp, with Gp-NO2 (4.41 eV) having the smallest energy gap. The density of states (DOS) analysis showed that the shape and functional group modifications affected the energy levels. Functionalization with electron-withdrawing (CN, NO2, COOH, SOH) or electron-donating (CH3) groups reduced the energy gap. To specifically target the removal of heavy metal ions, the Gp-NO2 ligand was selected for its high binding energy. Complexes of Gp-NO2-Cd, Gp-NO2-Hg, and Gp-NO2-Pb were optimized, and their properties were analyzed. The complexes were found to be planar, with metal-ligand bond distances within the range of 2.092→3.442 Å. The Gp-NO2-Pb complex exhibited the shortest bond length, indicating a stronger interaction due to the smaller size of Pb+ 2. The computed adsorption energy values (Eads) indicated the stability of the complexes, with values ranging from - 0.035 to -4.199 eV. Non-covalent interaction (NCI) analysis was employed to investigate intermolecular interactions in Gp-NO2 complexes. The analysis revealed distinct patterns of attractive and repulsive interactions, providing valuable insights into the binding preferences and steric effects of heavy metals.

The Effect of Hole Geometry on the Nonlinear Nanomechanics of γ-Graphyne Structures: A Finite Element Analysis.

Graphyne is a material that has unique mechanical properties, but little is known about how these properties change when the material has holes. In this work, the effect of hole geometry, considering circular, triangle, and rhombus hole configurations, on the mechanical nonlinear response of γ-graphyne structures is studied. Graphyne, graphdiyne, graphyne-3, and graphyne-4 structures are under investigation. An efficient nonlinear finite element analysis (FEA) method is adequately implemented under large deformations for this purpose. The study varied the size and shape of the holes to understand how these changes affect the nanostructure's mechanical response. The results indicate that the hole geometry significantly impacts the mechanical nonlinear response of γ-graphyne structures. The holes' size and shape affect the structures' elastic behavior, deformation, and strength. The findings can be used to optimize the design of γ-graphyne structures for specific mechanical applications. The study highlights the importance of considering the hole geometries in the design and fabrication of these materials.

Electronic, Thermal and Mechanical Properties of Carbon and Boron Nitride Holey Graphyne Monolayers.

In a recent experimental accomplishment, a two-dimensional holey graphyne semiconducting nanosheet with unusual annulative π-extension has been fabricated. Motivated by the aforementioned advance, herein we theoretically explore the electronic, dynamical stability, thermal and mechanical properties of carbon (C) and boron nitride (BN) holey graphyne (HGY) monolayers. Density functional theory (DFT) results reveal that while the C-HGY monolayer shows an appealing direct gap of 1.00 (0.50) eV according to the HSE06(PBE) functional, the BNHGY monolayer is an indirect insulator with large band gaps of 5.58 (4.20) eV. Furthermore, the elastic modulus (ultimate tensile strength) values of the single-layer C- and BN-HGY are predicted to be 127(41) and 105(29) GPa, respectively. The phononic and thermal properties are further investigated using machine learning interatomic potentials (MLIPs). The predicted phonon spectra confirm the dynamical stability of these novel nanoporous lattices. The room temperature lattice thermal conductivity of the considered monolayers is estimated to be very close, around 14.0 ± 1.5 W/mK. At room temperature, the C-HGY and BN-HGY monolayers are predicted to yield an ultrahigh negative thermal expansion coefficient, by more than one order of magnitude larger than that of the graphene. The presented results reveal decent stability, anomalously low elastic modulus to tensile strength ratio, ultrahigh negative thermal expansion coefficients and moderate lattice thermal conductivity of the semiconducting C-HGY and insulating BN-HGY monolayers.

Computational Studies on Diverse Characterizations of Molecular Descriptors for Graphyne Nanoribbon Structures.

Materials made of graphyne, graphyne oxide, and graphyne quantum dots have drawn a lot of interest due to their potential uses in medicinal nanotechnology. Their remarkable physical, chemical, and mechanical qualities, which make them very desirable for a variety of prospective purposes in this area, are mostly to blame for this. In the subject of mathematical chemistry, molecular topology deals with the algebraic characterization of molecules. Molecular descriptors can examine a compound's properties and describe its molecular topology. By evaluating these indices, researchers can predict a molecule's behavior including its reactivity, solubility, and toxicity. Amidst the captivating realm of carbon allotropes, γ-graphyne has emerged as a mesmerizing tool, with exquisite attention due to its extraordinary electronic, optical, and mechanical attributes. Research into its possible applications across numerous scientific and technological fields has increased due to this motivated attention. The exploration of molecular descriptors for characterizing γ-graphyne is very attractive. As a result, it is crucial to investigate and predict γ-graphyne's molecular topology in order to comprehend its physicochemical characteristics fully. In this regard, various characterizations of γ-graphyne and zigzag γ-graphyne nanoribbons, by computing and comparing distance-degree-based topological indices, leap Zagreb indices, hyper leap Zagreb indices, leap gourava indices, and hyper leap gourava indices, are investigated.

Low-Temperature Layer-by-Layer Growth of Semiconducting Few-Layer γ-Graphyne to Exploit Robust Biocompatibility.

The sp-hybridized carbon network in single- or few-layer γ-graphyne (γ-GY) has a polarized electron distribution, which can be crucial in overcoming biosafety issues. Here, we report the low-temperature synthesis, electronic properties, and amyloid fibril nanostructures of electrostatic few-layer γ-GY. ABC stacked γ-GY is synthesized by layer-by-layer growth on a catalytic copper surface, exhibiting intrinsic p-type semiconducting properties in few-layer γ-GY. Thickness-dependent electronic properties of γ-GY elucidate interlayer interactions by electron doping between electrostatic layers and layer stacking-involved modulation of the band gap. Electrostatic few-layer γ-GY induces high electronic sensitivity and intense interaction with amyloid beta (i.e., Aß40) peptides assembling into elongated mature Aß40 fibrils. Two-dimensional biocompatible nanostructures of Aß40 fibrils/few-layer γ-GY enable excellent cell viability and high neuronal differentiation of living cells without external stimulation.

Performance Analysis of an α-Graphyne Nano-Field Effect Transistor.

Graphyne has attractive electronic properties that make it a possible replacement of silicon in FET technology. In FET technology, the goal is to achieve low power dissipation and lower subthreshold swing. In this study, we focused on achieving these goals and studied the electronic properties of α-graphyne nanoribbons. We simulated the transfer and output characteristics of an α-graphyne ballistic nanoribbon FET. We used the tight-binding model with nearest-neighbor approximation to obtain the band structure which gives the same band structure as the one found from the DFT. In order to simulate the I-V characteristics of the transistor we used the non-equilibrium Green's function (NEGF) formalism. The results show that the modeled FET can provide a high Ion/Ioff ratio and low subthreshold swing. We also studied the effects of defects as defects cannot be avoided in any practical device. The study shows that the Ion/Ioff ratio and subthreshold swing improves as defects are added, but the delay time and dynamic power dissipation worsen.

A DFT approach for finding therapeutic potential of graphyne as a nanocarrier in the doxorubicin drug delivery to treat cancer.

In the present work, the drug-loading efficacy of graphyne (GYN) for doxorubicin (DOX) drug is investigated for the first time by using density functional theory (DFT). Doxorubicin drug is effective in the cure of numerous types of cancer including bone cancer, gastric, thyroid, bladder, ovarian, breast, and soft tissue cancer. Doxorubicin drug prevents the cell division process by intercalating in the double-helix of DNA and stopping its replication. The optimized, geometrical, energetic, and excited-state characteristics of graphyne (GYN), doxorubicin drug (DOX), and doxorubicin-graphyne complex (DOX@GYN complex) are calculated to see how effective it is as a carrier. The DOX drug interacted with GYN with an adsorption-energy of -1.57 eV (gas-phase). The interaction of GYN with DOX drug is investigated using NCI (non-covalent interaction) analysis. The findings of this analysis showed that the DOX@GYN complex has weak forces of interaction. Charge transfer from doxorubicin drug to GYN during DOX@GYN complex formation is described by charge-decomposition analysis and HOMO-LUMO analysis. The increased dipole-moment (8.41 D) of the DOX@GYN in contrast with therapeutic agent DOX and GYN indicated that the drug will move easily in the biochemical system. Furthermore, the photo-induced electron-transfer process is explored for excited states, and it reveals that upon interaction, fluorescence-quenching will occur in the complex DOX@GYN. In addition, the influence of the positive and negative charge states on the GYN and DOX@GYN is also considered. Overall, the findings indicated that the GYN could be exploited as an effective drug-transporter for the delivery of doxorubicin drug. Investigators will be inspired to look at another 2D nanomaterials for drug transport applications as a result of this theoretical work.

Host-guest coupling to potentially increase the bio-accessibility of 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea by nanocarrier graphyne for brain tumor therapy, a comprehensive quantum mechanics study.

This study aimed to explore the potential of Host-Guest coupling with Nanocarrier graphyne (GPH) to enhance the bioavailability of the drug 1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea (LUM) for brain tumor therapy. The electronic, geometric, and excited-state properties of GPH, LUM, and the graphyne@1-(2-chloroethyl)-3-cyclohexyl-1-nitrosourea-complex (GPH@LUM-complex) were studied using DFT B3LYP/6-31G** level of theory. The results showed that the GPH@LUM-complex was stable with negative adsorption energy (-0.20 eV), and there was good interaction between GPH and LUM in the solvent phase. The weak interaction forces between the two indicated an easy release of the drug at the target site. The Frontier Molecular Orbitals (FMO), Charge Density Analysis (CDA), and Natural Bond Orbital (NBO) analysis supported LUM to GPH charge transfer during complex formation, and the Reduced Density Gradient (RDG) isosurfaces identified steric effects and non-bonded interactions. UV-visible examination showed the potential of the GPH@LUM-complex as a drug carrier with a blue shift of 23 nm wavelength in the electronic spectra. The PET process analysis revealed a fluorescence-quenching process, facilitating systematic drug delivery. The study concluded that GPH had potential as a carrier for delivering LUM, and different 2D nanomaterials could be explored for drug delivery applications. The theoretical study's findings may motivate researchers to investigate the practical applications of GPH@LUM-complex in oncology.

Theoretical Investigation of HER and OER Electrocatalysts Based on the 2D R-graphyne Completely Composed of Anti-Aromatic Carbon Rings.

Based on the DFT calculations, two-dimensional (2D) R-graphyne has been demonstrated to have high stability and good conductivity, which can be conducive to the relevant electrocatalytic activity of the material. Different from the poor graphene, R-graphyne, which is completely composed of anti-aromatic structural units, can exhibit certain HER catalytic activity. In addition, doping the TM atoms in Group VIIIB can be considered an effective strategy to enhance the HER catalytic activity of R-graphyne. Particularly, Fe@R-graphyne, Os@R-graphyne, Rh@R-graphyne and Ir@R-graphyne can exhibit higher HER catalytic activities due to the formation of more active sites. Usually, the shorter the distance between the TM and C atoms is, the better the HER activity of the C-site is. Furthermore, doping Ni and Rh atoms of Group VIIIB can significantly improve the OER catalytic performance of R-graphyne. It can be found that ΔGO* can be used as a good descriptor for the OER activities of TM@R-graphyne systems. Both Rh@R-graphyne and Ni@R-graphyne systems can exhibit bifunctional electrocatalytic activities for HER/OER. In addition, all the relevant catalytic mechanisms are analyzed in detail. This work not only provides nonprecious and highly efficient HER/OER electrocatalysts, but also provides new ideas for the design of carbon-based electrocatalysts.

Thermal Stability and Vibrational Properties of the 6,6,12-Graphyne-Based Isolated Molecules and Two-Dimensional Crystal.

We report the geometry, kinetic energy, and some optical properties of the 6,6,12-graphyne-based systems. We obtained the values of their binding energies and structural characteristics such as bond lengths and valence angles. Moreover, using nonorthogonal tight-binding molecular dynamics, we carried out a comparative analysis of the thermal stability of 6,6,12-graphyne-based isolated fragments (oligomer) and two-dimensional crystals constructed on its basis in a wide temperature range from 2500 to 4000 K. We found the temperature dependence of the lifetime for the finite graphyne-based oligomer as well as for the 6,6,12-graphyne crystal using a numerical experiment. From these temperature dependencies, we obtained the activation energies and frequency factors in the Arrhenius equation that determine the thermal stability of the considered systems. The calculated activation energies are fairly high: 1.64 eV for the 6,6,12-graphyne-based oligomer and 2.79 eV for the crystal. It was confirmed that the thermal stability of the 6,6,12-graphyne crystal concedes only to traditional graphene. At the same time, it is more stable than graphene derivatives such as graphane and graphone. In addition, we present data on the Raman and IR spectra of the 6,6,12-graphyne, which will help distinguish it from the other carbon low-dimensional allotropes in the experiment.

Controlled supramolecular interactions for targeted release of Amiodarone drug through Graphyne to treat cardiovascular diseases: An in silico study.

In the current study, the drug loading ability of graphyne (GY) for the amiodarone (AMD) drug is investigated for the first time. The efficacy of GY as a carrier for amiodarone (a cardiovascular drug) is evaluated by calculating its electronic, energetic, optimized, and excited state properties with help of the density functional theory (DFT). The AMD drug interacted with the GY molecule with an adsorption energy of about -0.19 eV (gas-phase) and -1.92 eV (aqueous phase), suggesting that the AMD@GY complex is stable in water-phase. The HOMO (highest-occupied molecular-orbital) of the AMD@GY complex is concentrated on the AMD drug while the LUMO (lowest-unoccupied molecular-orbital) is centralized on GY with absolute charge separation, indicating charge transfer will occur between AMD and GY. The charge-transfer process is further studied with the aid of charge-decomposition analysis (CDA). The non-covalent interaction analysis (NCI) exposed that non-covalent forces exist between the GY carrier and AMD drug. These non-covalent forces between AMD drug and GY carrier play a significant role in drug unloading at the targeted or diseased site. Likewise, the calculations at excited-state, charge-state (+1 and -1) influence on GY and AMD@GY complex structures, and photo-induced electron transfer analysis (PET) are also studied for the graphyne-based drug-delivery system. According to PET and electron-hole analysis, fluorescence-quenching will occur upon interaction. Overall, it is concluded that graphyne can be exploited as a drug carrier for amiodarone drug delivery. Researchers will be fascinated to look at alternative 2D nanomaterials for drug delivery applications as a result of this theoretical work.

Anab initiostudy of catechol sensing in pristine and transition metal decoratedγ-graphyne.

Catechol is a toxic biomolecule due to its low degradability to the ecosystem and unpredictable impact on human health. In this work, we have investigated the catechol sensing properties of pristine and transition metal (Ag, Au, Pd, and Ti) decoratedγ-graphyne (GY) systems by employing the density functional theory and first-principles molecular dynamics approach. Simulation results revealed that Pd and Ti atom is more suitable than Ag and Au atom for the decoration of the GY structure with a large charge transfer of 0.29e and 1.54e from valence d-orbitals of the Pd/Ti atom to the carbon-2p orbitals of GY. The GY + Ti system offers excellent electrochemical sensing towards catechol with charge donation of 0.14e from catechol O-p orbitals to Ti-d orbitals, while the catechol molecule is physisorbed to pristine GY with only 0.04e of charge transfer. There exists an energy barrier of 5.19 eV for the diffusion of the Ti atom, which prevents the system from metal-metal clustering. To verify the thermal stability of the sensing material, we have conducted the molecular dynamics simulations at 300 K. We have reported feasible recovery times of 2.05 × 10-5s and 4.7 × 102s for sensing substrate GY + Pd and GY + Ti, respectively, at 500 K of UV light.

Recent advances on graphyne and its family members as membrane materials for water purification and desalination.

Graphyne and its family members (GFMs) are allotropes of carbon (a class of 2D materials) having unique properties in form of structures, pores and atom hybridizations. Owing to their unique properties, GFMs have been widely utilized in various practical and theoretical applications. In the past decade, GFMs have received considerable attention in the area of water purification and desalination, especially in theoretical and computational aspects. More recently, GFMs have shown greater prospects in achieving optimal separation performance than the experimentally derived commercial polyamide membranes. In this review, recent theoretical and computational advances made in the GFMs research as it relates to water purification and desalination are summarized. Brief details on the properties of GFMs and the commonly used computational methods were described. More specifically, we systematically reviewed the various computational approaches employed with emphasis on the predicted permeability and selectivity of the GFM membranes. Finally, the current challenges limiting their large-scale practical applications coupled with the possible research directions for overcoming the challenges are proposed.

Construction of Nitrogen-abundant Graphyne Scaffolds via Mechanochemistry-Promoted Cross-Linking of Aromatic Nitriles with Carbide Toward Enhanced Energy Storage.

The 2D graphyne-related scaffolds linked by carbon-carbon triple bonds have demonstrated promising applications in the field of catalysis and energy storage due to their unique features including high conductivity, permanent porosity, and electron-rich properties. However, the construction of related scaffolds is still mainly limited to the cross-linking of CaC2 with multiple substituted aromatic halogens and there is still a lack of efficient methodology capable of introducing high-concentration heteroatoms within the architectures. The development of alternative and facile synthesis procedures to afford nitrogen-abundant graphyne materials is highly desirable yet challenging in the field of energy storage, particularly via the facile mechanochemical procedure under neat and ambient conditions. Herein, graphyne materials with abundant nitrogen-containing species (nitrogen content of 6.9-29.3 wt.%), tunable surface areas (43-865 m2  g-1 ), and hierarchical porosity are produced via the mechanochemistry-driven pathway by deploying highly electron-deficient multiple substituted aromatic nitriles as the precursors, which can undergo cross-linking reaction with CaC2 to afford the desired nitrogen-doped graphyne scaffolds efficiently. Unique structural features of the as-synthesized materials contributed to promising performance in supercapacitor-related applications, delivering high capacitance of 254.5 F g-1 at 5 mV s-1 , attractive rate performance, and good long-term stability.

Unfurling Anion-π Interactions Involving Graphynes.

Ever since the inception of anion-π interactions, their nature and functional relevance have intrigued researchers. We address the twin challenge of elucidation of the role of extended conjugation and design of all-carbon neutral anion receptors by computations on the anion-π complexes of the halide ions with graphynes. Leveraging on the extended π-conjugation effects, we unfurl the functional relevance of graphynes as anion receptors using descriptors such as electrostatic potential, quadrupole moments, molecular polarizabilities and binding energies. Further, employing natural energy decomposition analysis, we assert that anion-π interactions are not merely dominated by electrostatic interactions. The polarization components do indeed play a crucial role in governing the binding of the anions to the graphynes.