Pristine Graphyne Research Articles

Evaluate the potential adsorption of graphynes (perfect and doped) for nitrogen mustard gas: A first principles study

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 BN linkages for CC 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.

First-Principles Studies of Three Pristine and BN-Doped Graphyne Allotropes

First-Principles Studies of Three Pristine and BN-Doped Graphyne Allotropes

The drug delivery of Ciclopirox anticancer by γ-graphyne and its boron nitride analogue: electronic study via DFT

ABSTRACT 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.

Favipiravir drug molecule adsorbed graphyne as a promising drug delivery vehicle for anti-viral treatment

This study utilized density functional theory (DFT) calculations to explore the potential of pristine graphyne as a drug delivery vehicle for the antiviral drug favipiravir. Favipiravir molecule absorbed on the pristine graphyne surface with the lowest binding energy (−1.485 eV) and can be inferred that chemisorption of favipiravir molecule occurred on pure graphyne surface. Interestingly, a significant reduction in band gap is noted after favipiravir adsorption that enhances the electrical conductivity. From the Bader charge transfer analysis, a transfer of 0.013 e charge has been observed from the graphyne surface to the drug molecule. A significant increase in the binding energy (−0.066 eV) in comparison to the non-acidic condition shows that the interaction between the favipiravir molecule and the pristine graphyne weakens in an acidic environment. Consequently, the graphyne can effectively release the drug molecule to the intended location. Outcome of this study confirmed the ability of pristine graphyne as a favipiravir drug delivery vehicle for the treatment of antiviral diseases. Moreover, the desorption of the drug molecule in the target site occurs very rapidly and demonstrates the potential of the pristine graphyne as a drug delivery vehicle for transporting the favipiravir drug molecule.

Copper decorated graphyne as a promising nanocarrier for cisplatin anti-cancer drug: A DFT study

Novel two-dimensional carbon allotrope namely pristine graphyne and Cu-doped graphyne have been proposed and their potentiality as nanocarriers for cisplatin anticancer drug is demonstrated theoretically. Based on binding energy calculation, it has been noted that pristine graphyne (-0.550 eV), as well as Cu-decorated graphyne (-0.750 eV), are suitable candidates for drug delivery, as the binding energy falls in the physisorption range. A charge transfer of 0.012 e from Cu-decorated graphyne is observed, which results in charge depletion in the Cu-doped graphyne system. The loss is mainly encountered by Cu (0.012 e) atom. Further, binding energy has been recalculated in the biological environment (acidic conditions) to infer drug release phenomena. A decrease in binding energy (-0.012 eV) and low recovery time reflects the successful release of cisplatin drug inside the body. Ab initio molecular dynamics simulation ensured that Cu-doped graphyne is stable at 300 K and can be used as nanocarrier for cisplatin drug. Interestingly, desorption temperature is slightly higher than body temperature and it comes closer to body temperature under acidic environment and this suggests cisplatin drug is certainly absorbed within the human body. Our theoretical predictions will inspire the experimentalist to design graphyne-based drug delivery systems.

Exploring the thermal conductivity and mechanical properties of BN-doped graphyne.

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 1K-1200K and 107s-1-109s-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 900K) 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.

Thioguanine adsorption on the γ-graphyne and its boron nitride analogue as promising drug delivery system: Electronic study via DFT

Thioguanine adsoption on the γ- graphyne and its boron nitride analogue as promising drug delivery system: Electronic study via DFT. • This paper primarily aims to conduct a theoretical evaluation of TG/GY and TG/BNY complexes to realize whether TG could be delivered in a controlled manner. • The quantum theory of atoms-in-molecules (QTAIM) was adopted to investigate the drug-nanosheet interactions. • BNY was ensured to be capable of serving as a candidate carrier of TG in drug delivery applications. There exists a significant body of research on the development of novel systems for drug delivery. This paper exploits graphyne (GY) as an allotrope of carbon to introduce pristine and BN-analog of GY (BNY) nanosheets. The interactions of GY and BNY with Thioguanine (TG) (anticancer drug) were examined through Density Functional Theory (DFT) calculations. Pristine GY was found to strongly enhance the TG adsorption potential through N and B atoms. Moreover, the Ultraviolet–Visible (UV–vis) analysis revealed a redshift to lower energy levels (i.e., higher wavelengths). In addition, the TG/BNY system was observed to be chemically reactive and thus suitable for drug bonding with the adsorptive site. Furthermore, the Atoms-In-Molecules (AIM) analysis was carried out to obtain a deeper understanding of the drug-nanosheet complexes, and strong interactions of TG and BNY were observed. As a result, it was ensured that BNY is capable of serving as a candidate carrier for TG in drug delivery applications.

AsH3 adsorption on pristine, P-doped and Ga-doped graphynes: a DFT Study

AsH3 adsorption on pristine, P-doped and Ga-doped graphynes: a DFT Study

Synergistic Effect of Coordination Fields and Hydrosolvents on the Single-Atom Catalytic Property in H2O2 Synthesis: A Density Functional Theory Study

The design of high-performance single-atom catalysts (SACs) for two-electron oxygen reduction reaction (2e– ORR) is of great importance for the large-scale commercial application of H2O2 electrosynthesis. Herein, utilizing the combination of density functional theory (DFT) calculation and ab initio molecular dynamic (AIMD) simulation, an effective computational framework was built to identify the critical role of coordination fields and hydrosolvents in the 2e– ORR catalytic properties of SAC-based two substrates [pristine γ-type graphyne (γ-GY) and B-doped γ-GY]. The screening calculations of 168 TM@(B-doped) γ-GY (TM = transition metal) revealed that both Co@B1-2-γ-GY and Pd@B3-2-γ-GY feature outstanding catalytic properties with low overpotentials (0.06, 0.02 V) and excellent stability. The electronic structure results uncovered that viewing from the coordination field, electron-deficient boron atoms can manipulate the electron back-donation effect (d → π2p*) of the TM–O bond to mediate the H2O2 property. Solvent effect calculations revealed that the hydrogen-bond (H-bond) framework plays an important role in the high selectivity of H2O2 by facilitating the H transfer from water (>99.9 and 98.6% for Co@B1-2-γ-GY and Pd@B3-2-γ-GY), shedding light on the higher accuracy of an explicit solvent than that of an implicit one. This work will provide one way to better design high-selectivity SACs for H2O2 synthesis effectively.

Theoretical investigation of Br2 and Cl2 detection by the pristine and Co-doped graphyne

The Br2 and Cl2 interaction with the intrinsic and Co-doped graphyne nanosheets has been explored by density functional theory calculations. Two vertical and parallel configurations were identified for Br2 and Cl2 adsorption. Calculations showed that the adsorption of Br2 was stronger than Cl2 on the graphyne nanosheet. Neither Br2 nor Cl2 could make serious changes to the HOMO–LUMO gap (Eg) and electrical resistance of pristine sheet. By manipulating the structure of pristine graphyne by Co atom, its reactivity and sensitivity dramatically improved toward Br2 and Cl2 gases. Compared to the Cl2, the Br2 much more decreases the electrical resistance and Eg of the Co-doped graphyne (~ −40.25%). Thus, the Co-doped graphyne may selectively recognize the Br2 gas in the presence of Cl2. The computed recovery time value for Br2 from the surface of the Co-doped graphyne is 36.4 s, which shows that the graphyne, as a sensor, benefits from a short recovery time to detect Br2.

Developments in Synthesis and Potential Electronic and Magnetic Applications of Pristine and Doped Graphynes.

Doping and its consequences on the electronic features, optoelectronic features, and magnetism of graphynes (GYs) are reviewed in this work. First, synthetic strategies that consider numerous chemically and dimensionally different structures are discussed. Simultaneous or subsequent doping with heteroatoms, controlling dimensions, applying strain, and applying external electric fields can serve as effective ways to modulate the band structure of these new sp2/sp allotropes of carbon. The fundamental band gap is crucially dependent on morphology, with low dimensional GYs displaying a broader band gap than their bulk counterparts. Accurately chosen precursors and synthesis conditions ensure complete control of the morphological, electronic, and physicochemical properties of resulting GY sheets as well as the distribution of dopants deposited on GY surfaces. The uniform and quantitative inclusion of non-metallic (B, Cl, N, O, or P) and metallic (Fe, Co, or Ni) elements into graphyne derivatives were theoretically and experimentally studied, which improved their electronic and magnetic properties as row systems or in heterojunction. The effect of heteroatoms associated with metallic impurities on the magnetic properties of GYs was investigated. Finally, the flexibility of doped GYs’ electronic and magnetic features recommends them for new electronic and optoelectronic applications.

Thermoelectric Properties of Pristine Graphyne and the BN-Doped Graphyne Family.

In this paper, we have investigated the thermoelectric properties of BN-doped graphynes and compared them with respect to their pristine counterpart using first-principles calculations. The effect of temperature on the thermoelectric properties has also been explored. Pristine γ-graphyne is an intrinsic band gap semiconductor and the band gap significantly increases due to the incorporation of boron and nitrogen atoms into the system, which simultaneously results in high electrical conductivity, a large Seebeck coefficient, and low thermal conductivity. The Seebeck coefficient for all these systems is significantly higher than that of conventional thermoelectric materials, suggesting their potential in thermoelectric applications. Among all the considered systems, the “graphyne-like BN sheet” has the highest electrical conductance and lowest thermal conductance, ensuring its superiority in thermoelectric properties over the other studied systems. We find that a maximum full ZT of ∼6 at room temperature is accessible in the “graphyne-like BN sheet”.

CS2 adsorption on pristine and Al-doped graphynes: A DFT study

Sensitivity of graphyne CS2 gas was investigated. As CS2 approaches the graphyne, its adsorption releases 0.19 to 0.29 eV of energy, indicating a weak adsorption. Electronic analysis showed that the CS2 adsorption reduces the HOMO-LUMO energy gap (Eg) of the pure graphyne from 2.57 to 2.40 eV (~-6.6%), which can be concluded that the electrical conductivity of the nanosheet do not change significantly. Al doping makes graphyne more reactive and sensitive to CS2, the adsorption energy of CS2 on the Al-doped graphyne was predicted to be 1.53 to 1.75 eV. The CS2 adsorption reduces the Eg of Al-doped sheet from 2.12 to 1.45 eV (~-31.6%), which can be concluded that the sheet's electrical conductivity has increased. Thus, the Al-doped sheet can generate electrical signals when the CS2 molecules approach, which can be said that it may be a good choice for the production of CS2 chemical sensors.

DFT-D3 calculations of the charge-modulated CO2 capture of N/Sc-embedded graphyne: Compilation of some factors

The increasing greenhouse gases, including CO2 in the atmosphere, have a devastating effect on the ecosystem. Therefore, scientists are trying to provide new materials for CO2 capture, storage, and conversion. In this work, we consider CO2 capture behavior of N, Sc, and Sc/N embedded graphyne (GY) for neutral and negatively charge states by DFT-D3 calculations. It is found that in the most stable structures with single N (N1-GY) or Sc (Sc1-GY) and in Sc/N-GY, N and Sc atoms prefer to stand in the chains and the H1 sites of GY, respectively. Eads values of CO2 onto pristine GY (PGY) and N1-GY in neutral or negatively charged states are low (physisorption) (‒0.212 to ‒0.286 eV); while insertion of Sc causes that CO2 capture improves even in neutral state to ‒0.726 eV for Sc1-GY and promotes considerably in ‒2 e negatively charged Sc/N-GY1 up to ‒3.186 eV. It can say that synergistic effect of N and Sc insertion and ‒2 e negatively charged on the PGY causes a 1500% increasing of CO2 adsorption energy. Evaluation of the CO2 adsorption/desorption mechanism for negatively charged Sc1-GY and Sc/N-GY1 structures represents that choosing the proper charge state is very effective on the CO2 regeneration process.

Evaluating the electronic sensitivity of pristine, B, and Si doped graphyne to methanol: DFT study

The reactivity and electronic sensitivity of pristine, B-doped graphyne (BG) and Si-doped graphyne (SiG) sheet toward the methanol gas adsorption were explored by calculation of density functional theory. It was discovered that the pristine graphyne unstably adsorbs the methanol gas with a −6.28 kcal mol−1 adsorption strength. Also, the evaluated electronic properties of pristine graphyne are not sensitive toward methanol gas. The doping process improves neither the reactivity nor sensitivity of graphyne to methanol, while the Si-doping enhances the reactivity and has a significant impact on the sensitivity. The HOMO-LUMO gap of SiG considerably reduces from 2.59 to 2.04 eV via methanol adsorption, increasing the electrical conductivity. It indicates that the SiG sheet may be a promising electronic sensor for methanol detection, unlike the BG and pristine graphyne. Also, the adsorption of methanol on the SiG largely affects its work function which significantly alters the field emission electron current from its surface, demonstrating that it might also be a working function form of methanol detection sensor. The SiG sheet benefits from a quick recovery time of 1.38 ms for desorption of methanol.

Synergetic effects of metals in graphyne 2D carbon structure for high promotion of CO2 capturing

Structural and electronic properties of co-decorated graphyne (GY) by Sc and Cr atoms toward CO2 capture are investigated by DFT-D3 method. First, different configurations of Sc-Cr co-decorated GY (SCGY) are considered to find the best site and side of GY for SC and Cr atoms and structural, magnetic, and electronic properties of them are investigated. Then, the adsorption behavior of the best configurations toward CO2 capture is followed. Results show that in single Sc or Cr decorated GY, the best site for metals is the center of the 12-membered ring (H1) and Eads are −4.856 and −2.414 eV, respectively. In SCGY, the best site for Cr and Sc are H1 and H3 sites, but they lie in the opposite sides and Eads improves about 0.505 eV. In brief, Edas of CO2 for pristine GY (PGY), Sc-GY, Cr-GY, Sc-Cr-GY, Sc-Sc-GY, and Cr-Cr-GY are about −0.242, −0.717, −1.502, −0.795, −2.970 and −1.754 eV, respectively. Increasing of Eads due to the insertion of one or two metal atoms for some systems is about 3 to 12 times more than PGY, surprisingly. The best system can capture up to 19 CO2 molecules with Eads- of −0.516 eV/CO2 that is CO2 storage capacity of 55.66 wt%. These results show that co-decorated GYs with various metals, due to having synergistic effects, can be used as promising candidates for the CO2 capture, storage, detection, and removal applications in the future.

WITHDRAWN: Quantum chemical study on the potential application of pristine and BN-doped graphynes for carac drug detection

The reactivity and electronic sensitivity of the pristine and BN-doped graphynes (BN-G) are scrutinized toward anticancer carac drug in the basis of density functional theory calculations. The drug physically adsorbs via its H atoms on the –C≡C– linkages of the pristine graphyne with adsorption energy about -4.7 kcal/mol and has no impact on its conductance. Replacing a –C≡C– linkage by isoelectronic –B=N– linkage significantly increases the reactivity of graphyne toward the carac drug so that the adsorption energy becomes -22.4 kcal/mol. By the adsorption of carac on the BN-G, the charge transfer is great (∼ 0.23 |e|) from the carac to the sheet, generating a new occupied state higher than the HOMO level of bare BN-G by about 1.31 eV. As a result, the HOMO-LUMO gap of BN-G meaningfully (∼ 45.8%) declines, increasing the electrical conductance which can make an electronic sign by the drug adsorption. The results suggest that the BN-doping makes the graphyne an appropriate candidate for application in carac sensors. Also, a short recovery time about 2.5 s is predicted for BN-G.

Mustard gas adsorption on the pristine and BN-doped graphynes: A computational study

The electronic sensitivity and reactivity of pristine, and BN doped graphyne (BNG) are scrutinized toward mustard gas using DFT calculations. The mustard gas weakly adsorbs via its Cl atom on the graphyne with adsorption energy about -3.1 kcal/mol and has no effect on its electrical conductivity. Replacing –C≡C– linkages with isoelectronic –BN– linkages increases the HOMO-LUMO gap (Eg) and decreases the work function and reactivity of graphyne. By mustard adsorption, the Eg of BNG decreases from 2.24 to 1.12 eV, increasing the electrical conductivity. Also, the BNG work function is considerably affected, changing the field emission electron current. Finally, a short recovery time about 0.03 s at room temperature is predicted for the mustard desorption from the surface of BNG. We also showed that the electrical conductivity change relates to the mustard concentration. The results indicate that the BNG may be a promising sensor for mustard gas.

First-principles study of stability, electronic structure and quantum capacitance of B-, N- and O-doped graphynes as supercapacitor electrodes

The structures, stability, electronic properties, and quantum capacitance (Cq) of α-, β-, and γ-graphyne monatomic layer doped with B, N, and O atoms, respectively, were studied using density functional theory. Two different doping sites (i.e. D1 and D2) were considered. Upon replacement of C atoms in the three graphynes with B and N atoms, the structure of graphynes was minimally distorted. This change was mainly manifested as a negligible adjustment of bond length around the doped atoms and lattice constant. However, with O atom doping, the structural distortion of graphynes was obvious in the majority of cases. The doping of these atoms significantly improved the electronic state of the original graphyne near the Fermi level, thereby improving graphyne Cq. Pristine graphynes with large pores and specific surface area exhibited better Cq performance than that of pure graphene. Cq of graphynes doped with B, N, and O showed significant advantage over that of doped graphene, especially that of α-, β-, and γ-graphyne with B doping at D1 and α-graphyne with O doping at D1. Interestingly, β-graphyne with O doping at D2 showed a considerably symmetrical Cq. Thus, element-doped graphynes have great potential as electrode materials for supercapacitors.

Multiple CO2 capture in pristine and Sr-decorated graphyne: A DFT-D3 and AIMD study

Recent advances in two-dimensional carbon allotropes and their applications as efficient CO2 capture materials can decrease effect of CO2 on the global weather changes. In current study, influence of strontium on the structural and electronic properties of a new allotrope of carbon, graphyne (GY), toward promotion of CO2 capture capacity were investigated using DFT-D3 calculations. Various sites for Sr decoration in GY frame were probed. Then, we investigated the best site and direction for adsorption of CO2 on the structures. Results show that the best site is 1.740 Å above the center of the 12-membered ring with the adsorption energy of −3.034 eV. It is very more than bulk cohesive energy of Sr (about −1.72 eV/atom), therefore, aggregation of the Sr atoms is hindered on the GY sheet. Also, for pristine GY, 12-membered ring and for Sr-decorated GY, top of Sr atom are the best sites for CO2 trapping with adsorption energies of −0.252 and −0.425 eV, respectively. Thermal stability of the structures at room temperature was confirmed by Ab initio molecular dynamics (AIMD) simulation. Adding of CO2 molecules on the pristine and Sr-decorated GY shows that three and seven CO2 molecules can adsorb on one side of the GY sheet with the average adsorption energy of −0.260 and −0.478 eV/CO2, respectively. Therefore, CO2 capture capacity is estimated to be as high as 31.68 wt% for the Sr-decorated GY. This study shows that Sr-decorated GY can be used as a hopeful candidate for the CO2 capture applications in the future.