Al12N12 Nanocage Research Articles

Exploring the interaction of ionic liquids with Al12N12 and Al12P12 nanocages for better electrode-electrolyte materials in super capacitors

For designing better energy storage devices, the interfacial interaction between ILs and nanostructure is a prerequisite. In the present study, the interaction of ionic liquids such as [EMIm]+[X]− on Al12N12 and Al12P12 nanocages has been investigated using DFT theory. The complexes of Al12P12 nanocage exhibit higher values of adsorption energies than those of Al12N12. The adsorption energies of IL-complexes range from −38.9 to −63.6 kcal/mol. Non-covalent interaction (NCI) and quantum theory of atoms in molecules (QTAIM) analyses revealed non-covalent interactions between the ionic liquids and nanocages. NBO analysis shows charge transfer between the ionic liquids and Al12N12 and Al12P12 nanocages, which results in significant enhancement of dipole moment values of IL-complexes. [EMI]+ [X]−@Al12P12 complexes show higher dipole moment values than those of [EMI]+ [X]−@Al12N12 complexes. FMO analysis depicts a decrease in the HOMO-LUMO energy gap of IL-complexes, enhancing the electrical conductivity of these complexes. Furthermore, the calculated quantum molecular descriptors show that ILs adsorbed Al12N12 complexes are less reactive than ILs adsorbed Al12P12 nanocages. Thermodynamic properties revealed that the adsorption of ILs on Al12N12 and Al12P12 is an exothermic and spontaneous process. This study illustrates that the electronic properties of Al12N12 and Al12P12 nanocages are fine-tuned by the adsorption of ionic liquids. This study provides an efficient approach to design better electrode–electrolyte materials for super capacitors, fuel cells, ion batteries, and solar cells.

First-principles study of the adsorption behavior of Octyl-β-D-xyloside surfactant on pristine Al12N12 and B12N12 nanocages

The octyl-β-D-xyloside is a biosurfactant with well-known roles in membrane protein systems. Using an efficient delivery system for these biosurfactants is of primary importance. This paper investigates the potential application of Al12N12 and B12N12 nanocages as an electronic sensor for octyl-β-D-xyloside surfactant detection in the gas phase using density functional theory calculations. Our results show that the electronic properties of Al12N12 and B12N12 nanocages were significantly affected by the adsorption of the octyl-β-D-xyloside molecule. The adsorption energies and enthalpies predicted a thermodynamically favorable chemisorption process. The AIM analysis depicted the formation of normal and bifurcated hydrogen bonds between Al12N12 and B12N12 nanocages and octyl-β-D-xyloside. The existence of the inter/intra-molecular and also conventional and unconventional hydrogen bonds were also detected. Our finding revealed although both Al12N12 and B12N12 nanocages have the ability to detect and adsorb the octyl-β-D-xyloside but, the adsorption over the Al12N12 is not favorable due to the high recovery time. Whilst, the adsorption of the octyl-β-D-xyloside on the B12N12 nanocage through O3 position with less steric factor and the recovery time of 8.14×10−3 S, is the best adsorption site.

Adsorption behavior of anticancer drug on the aluminum nitride surface: Density functional theory evolution

We evaluated the detection of fluorouracil (5FU) by means of an AlN nanocage using density functional theory (DFT) calculations. Different drug sites, which contain oxygen, fluorine and oxygen atoms, were adsorbed on the surface of the AlN nanocage to achieve the most stable AlN/5FU state, and the most stable adsorption energy which is equal to −61.08 kJ/mol was related to the interaction of Al metal with a F atom of 5FU. It is also suggested that an electrostatic interaction is accompanied by the process of drug adsorption on the surface of the AlN nanocage. The electrical conductivity of the AlN nanocage is raised drastically up to 21.5% after the adsorption of 5FU on the surface of the AlN nanocage. This increase in the conductivity can be considered as a signal to detect the drug. Therefore, the work function of the AlN nanocage is reduced from 4.5 eV to 3.68 eV after the adsorption of 5FU. This reduction is induced by the instant bipolarity caused by the induction of a positive charge on the AlN nanocage as well as a negative charge on 5FU. The findings obtained from the aqueous medium analysis show that the 5FU/AlN complex is more stable in the aqueous phase than in the gas phase.

First example of lanthanum as dopant on Al12N12 and Al12P12 nanocages for improved electronic and nonlinear optical properties with high stability

The electronic and nonlinear optical (NLO) properties of lanthanum doped Al12N12 and Al12P12 nanocages were investigated. The endohedral and exohedral doping of lanthanum were explored. The stability and structure of doped Al12N12, and Al12P12 nanocages were estimated by calculating interaction energies and geometric parameters. The exohedral doping is more favorable as compared to endohedral doping, which is reflected by the interaction energies. The HOMO-LUMO energy gaps were reduced (0.89 eV) in lanthanum doped Al12N12 and Al12P12 nanocages. The density of state plots strongly support the formation of a new high-energy HOMO level. This new HOMO energy level might be responsible for the reduced HOMO-LUMO energy gap. The natural bond orbital (NBO) charge analysis supports the charge transfer from metal towards the respective nanocage. The first hyperpolarizability was remarkably enhanced as compared to the pristine Al12N12 and Al12P12 nanocages by lanthanum doping. The maximum first hyperpolarizability value (4.43 × 104 au) was obtained for isomer A of Al12N12 series. The present investigation will attract the scientific community in designing the high-performance NLO materials for hi-tech NLO applications.

Monitoring and sensing of (HF)n linear chain for n = 1–4 on aluminum nitride nanocage in both gas and water phases; computational study

The interaction as well as the adsorption behavior of an (HF)n linear chain for n = 1–4 was inspected on an AlN nanocage using ab initio calculations to understand the ability of this material to monitor and sense the (HF)n in gas and water phases. The adsorption energies, optimized configurations, charge transfer, and the work function for this gas were calculated on the AlN nanocage surface. Also, the effect of the HF linear chain size was investigated on the adsorption energy and all of the electronic properties. According to the adsorption energy, the most stable configuration for the (HF)n on the AlN nanocage surface is the dimer form of the HF gas. Also, after the adsorption of the (HF)n on the AlN nanocage, the HOMO-LUMO gap decreased dramatically from 3.99 to 3.36 eV, leading to an increase in conductivity. Furthermore, the AlN nanocage can sense the (HF)n in the presence of many environmental pollutants.

Influence of bi-alkali metals doping over Al12N12 nanocage on stability and optoelectronic properties: A DFT investigation

Bi-alkali metal atoms (Li2, Na2, K2) doped Al12N12 nanocages with remarkable stability are achieved for the first-time using density functional theory. Bi-alkali doping is a highly efficient technique to bring high stability as compared to single alkali metal atom doping. It is revealed that bi-alkali metal atoms doping significantly reduced the wide HOMO-LUMO energy gap (3.93 eV) of pure Al12N12 nanocage to 0.74–1.67 eV. The reduction in HOMO-LUMO energy gap is due to the formation of new HOMO energy levels having diffused excess electrons which is further confirmed by the PDOS and TDOS plots. The bi-alkali metal atoms doped Al12N12 nanocages exhibit remarkable nonlinear optical response. The highest first hyperpolarizability of 1.2 × 105 au is observed for K2@Ntop. Clearly, the doping of high atomic number atoms brings larger hyperpolarizabilities, while the non-monotonic trend is observed for M2@b66 series where Na2@b66 has a large hyperpolarizability value. These fascinating results will be helpful for achieving the potential applications of inorganic Al12N12 nanocages in the optoelectronic devices and high performance nonlinear optical materials.

Exploring Li4N and Li4O superalkalis as efficient dopants for the Al12N12 nanocage to design high performance nonlinear optical materials with high thermodynamic stability

The influence of superalkalis (Li4N and Li4O) doping on the structural, electrical, optical and nonlinear optical properties of the Al12N12 nanocage has been theoretically investigated through density functional theory. The research findings show the strong impact of the superalkalis over the Al12N12 nanocage. The doping of superalkalis significantly reduced the HOMO-LUMO energy gap up to 50.75% compared to the pristine Al12N12 nanocage due to the formation of a new HOMO energy levels. All isomers possess diffuse excess electrons and are electrides in nature. The results also revealed the higher stability (interaction energies of up to −118.49 kcal/mol) and deep ultraviolet transparency of the studied isomers. Furthermore, superalkali doping dramatically enhanced the nonlinear optical response of the Al12N12 nanocage. The largest first hyperpolarizability of 5.7 × 104 au is achieved for isomer A of the Li4N@Al12N12 series. This outstanding increase in the NLO response is attributed to the small transition energies (1.27–2.73 eV) and charge transfer from the superalkali towards the nanocage. AIM and NCI analysis were also performed to investigate the nature of intermolecular interactions between the superalkali and Al12N12 nanocage. AIM topological analysis revealed that a closed shell electrostatic interaction is dominant. These findings offer an insight into designing and fabricating nonlinear optical materials with exceptional features for their widespread applications in optoelectronics.

Molecular modeling investigation of adsorption of Zolinza drug on surfaces of the B12N12 and Al12N12 nanocages

Molecular modeling investigation of adsorption of Zolinza drug on surfaces of the B12N12 and Al12N12 nanocages

Adsorption of alprazolam drug on the B12N12 and Al12N12 nano-cages for biological applications: A DFT study

In this study, density functional theory (DFT) calculations were used to investigate the interaction of the B 12 N 12 and Al 12 N 12 nano-cages with alprazolam (ALP) in the gas phase and water at the B3LYP/6-31G(d,p) level of the theory. According to the obtained results, B 12 N 12 nano-cage can be able to form a more stable complex with ALP in comparison to Al 12 N 12 . The stability of ALP/B 12 N 12 and ALP/Al 12 N 12 complexes was increased in the water as a simulation of the body condition. Natural bond orbital (NBO) analysis revealed an effective charge transfer from the nitrogen atoms of ALP to the boron atoms of nano-cages. Quantum theory of atoms in molecules (QTAIM) analysis indicated that the non-covalent interactions between Al 12 N 12 and ALP are the main driving force in the complex formation, whereas ALP/B 12 N 12 interaction is mainly electrostatic and partial covalent in nature. Moreover, there is an intra-molecular hydrogen bond between nitrogen atom of the nano-cages and hydrogen atom of ALP. Finally frontier molecular orbital (FMO) analysis was performed to get a better insight of the reactivity and stability of ALP/nano-cage complexes in the gas phase and water. Based on FMO analysis, B 12 N 12 nano-cage is a better biosensor for the detection of ALP drug in comparison to Al 12 N 12 due to the higher changes in its band gap. • The adsorption of alprazolam drug on B 12 N 12 and Al 12 N 12 nano-cages was studied by using DFT calculations. • B 12 N 12 and Al 12 N 12 nano-cages can be potential materials for detection or removal of alprazolam residue from aquatic environments. • B 12 N 12 nan-cage is a better biosensor for alprazolam drug molecule in comparison with Al 12 N 12 nano-cage.

Exploration of adsorption behavior, electronic nature and NLO response of hydrogen adsorbed Alkali metals (Li, Na and K) encapsulated Al12N12 nanocages

Due to the increasing demand of Al[Formula: see text]N[Formula: see text] in optoelectronics and sensing materials, we intended to investigate the adsorption behavior, electronic nature and NLO response of hydrogen and different metals decorated Al[Formula: see text]N[Formula: see text] nanocages. Different systems are designed by hydrogen adsorption and encapsulation of metals (Li, Na and K) in Al[Formula: see text]N[Formula: see text]. Density functional theory at B3LYP functional with conjunction of 6-31G([Formula: see text], [Formula: see text] basis set is utilized in order to gain optimized geometries. Different calculations including linear and first-order hyperpolarizability are conducted at same level of theory. Instead of chemiosorption, a phyisosorption phenomenon is seen in all hydrogen adsorbed metal encapsulated Al[Formula: see text]N[Formula: see text] nanoclusters. The [Formula: see text] analysis confirmed the charge separation in hydrogen adsorbed metal encapsulated nanocages. Molecular electrostatic potential (MEP) analysis cleared the different charge sites in all the systems. Similarly, frontier molecular orbitals analysis corroborated the charge densities shifting upon hydrogen adsorption on metal encapsulated AlN nanocages. HOMO–LUMO band gaps suggest effective use of H2-M-AlN in sensing materials. Global indices of reactivity also endorsed that all hydrogen adsorbed metal encapsulated systems are better materials than pure Al[Formula: see text]N[Formula: see text] nanocage for sensing applications. Lastly, linear and first hyperpolarizability of H2-M-AlN nanocages are found to be greater than M-AlN and pure AlN nanocages. Results of these parameters recommend metal encapsulated nanocages as efficient contributors for the applications in hydrogen sensing and optoelectronic devices.

Chemical-sensing of Amphetamine drug by inorganic AlN nano-cage: A DFT/TDDFT study

The electronic sensitivity and reactivity of a pristine Si, Ga and Ge-doped Al24N24 nanocluster with AM drug were investigated using density functional theory (DFT). With adsorption energy of approximately −35.5 kcal/mol, AM drug was found to be adsorbed chemically on pristine Al24N24 nanocluster through its N-head and to exert no effects on the electrical conductivity of this cluster. Substituting Si, Ga and Ge atoms for Al atoms in Al24N24 nanocluster significantly elevates the reactivity of Al24N24 nanocluster respectively at predicted adsorption energies of approximately −24.05, −11.75 and −34.38 kcal/mol. Significant HOMO destabilization in Si-AlN nanocluster through AM drug adsorption increases the electrical conductivity of Si-AlN nanocluster while generating electrical signals and reduces its Eg from 2.17 to 1.35 eV. These signals are associated with the presence of AM drug in the environment. Therefore Si-doped Al24N24 nanocluster is found to constitute a promising electronic AM drug sensor. AM drug adsorption increases electron emission from the surface of this sensor and significantly reduces its work function. Significant effects of AM drug adsorption on the Fermi levels and work function of Si-AlN nanocluster make it an Φ–type candidate for AM drug sensors.

TD-DFT, NBO, AIM, RDG and Thermodynamic Studies of Interactions of 5-Fluorouracil Drug with Pristine and P-doped Al12N12 Nanocage

In the present study, the capability of the pristine and P-doped Al12N12 nanocage to deliver and detect of 5-Fluorouracil (5-FU) anticancer drug are investigated using the density functional theory (DFT) at the cam-B3LYP/6-31G(d, P) level of theory. The adsorption energy, thermodynamic parameters, natural bond orbital (NBO), atom in molecule theory (AIM), quantum parameters, reduced density gradient (RDG) and UV-visible spectrum for all selected models are calculated and results are analyzed. The values of adsorption energy (Eads) and thermodynamic parameters (ΔG and ΔH) for 5-FU@Al12N12 and 5-FU@Al12N11P complexes are negative and obtained results reveal that all adsorption processes are spontaneous and suitable to make a delivery of drug. The ΔΔG(sol) values of the all studied systems in the presence of water and ethanol solvent are positive and this property is favourable to shooting drug in biological system. The AIM, RDG, NBO calculated results indicate that the interaction between 5-FU drug and Al12N12 nanocage is weak covalent or strong electrostatic type. The bandgap energy of the 5-FU/Al12N12 nanocage complex alters slightly from original values, and so the pristine and P doped Al12N12 nanocage is not an excellent candidate for making a sensitive sensor for the 5-FU drug.

The computational quantum mechanical study of sulfamide drug adsorption onto X12Y12 fullerene-like nanocages: detailed DFT and QTAIM investigations

In the current work, the adsorption of sulfamide drug onto the exterior surface of four fullerene-like nanocages, including Al12N12, Al12P12, B12N12, and B12P12, was studied by employing density functional theory (DFT) and the quantum theory of atom in the molecule (QTAIM) calculations. Our calculations revealed that the sulfamide drug connects to the Al, B, P, and N atoms of Al12N12, Al12P12, B12N12, and B12P12 nanocages through the oxygen and hydrogen atoms with releasing energies of −47.27, –34.59, –28.13 and –9.45 kcal/mol, respectively. Upon the sulfamide drug adsorption onto the stated nanocages, the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were significantly changed, resulting in a decrease in the values of bandgap (E g) that caused enhance in their electrical conductivity. This trend illustrated that all the stated nanocages may be potential electronic sensors as well as suitable candidates for the delivery of sulfamide drug in the biological system. Finally, The QTAIM analysis was investigated for both types of structural aspects and electronic properties (such as ρ, "∇" ^"2" ρ, G(r), V (r) and H(r)) associated with adsorption of sulfamide molecule on the stated nanocages.

Response of inorganic Al12N12 nano-cage toward nitrosyl hydride: A computational study

The geometrical and electronic structures of adsorption of HNO on Al12N12 nanocage have been examined utilizing DFT computations by means of a (B3LYP-D) function with 6-31G* basis set. It was observed that HNO prefers to be adsorbed on the cage oxygen atom with −0.70 eV adsorption energy. This process of adsorption remarkably decreases the HOMO-LUMO gap (Eg) of the cage from 3.91 to 1.41 eV. The time-dependent density functional theory (TDDFT) indicates a high intensity peak in 390.29 nm in the steadiest complexes of HNO with Al12N12. The alteration in electronic attributes of the Al12N12 nanocage on adsorption of HNO is enough to consider it a potential sensor for the detection of HNO. The Al12N12 nanocage is Ф-type sensor and electronic sensor for HNO.

Density functional theory based molecular dynamics study on hydrogen storage capacity of C24, B12N12, Al12 N12, Be12O12, Mg12O12, and Zn12O12 nanocages

In the current study, the density functional theory calculations (DFT) were employed to determine the hydrogen storage properties of some nanoclusters including C24, B12N12, Al12 N12, Be12O12, Mg12O12, and Zn12O12. After full geometrical optimization of all nanocages under the DFT framework, we found that C24 and B12N12 were unstable structures even in case of incorporating only one hydrogen molecule to them due to positive obtained formation energy magnitudes while Al12N12 and Be12O12 were able to adsorb one hydrogen molecules and became thermodynamically unstable for more than one hydrogen molecule. Also, Mg12O12 and Zn12O12 were capable of storing up to 4 hydrogen molecules according to negative achieved formation energies. Also, calculated bulk modulus revealed that when all studied structures stored H2 molecules the bulk modulus decreased compared to pristine nanoclusters. The highest reduction in bulk modulus was 10% which occurred in C24 while storing 5H2. Furthermore, the adsorption properties of these nanocages were considered using DFT and the results showed that Zn12O12 was a stronger adsorbent for H2 in comparison to the rest of the studied nanocages.

Hydrogen abstraction of methanimine by X12N12 (X = B, Al) nanoclusters: a DFT study

In this work, dissociative adsorption of methanimine (CH2NH) on the surface of B12N12 and Al12N12 nanoclusters is studied at wB97XD/6-31G(d) computational level. The results indicate that the CH2NH molecule is adsorbed on the surface of studied nanocages with remarkable adsorption energies and noticeable charge transfer. The main reaction channel generated a HCN molecule and two hydrogen atoms on a cage. It is predicted that the Al12N12 nanocage is the more suitable catalyst for the disintegration of CH2NH than B12N12. The results of the present study may be useful for extensive usage of BN and AlN nanostructures as a catalyst for dissociation of imines.

DFT and TD-DFT study of the adsorption and detection of sulfur mustard chemical warfare agent by the C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages

In the present research, the interaction of sulfur mustard, a chemical warfare agent, with the surface of C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages was studied using the dispersion corrected density function theory (DFT-D3) method. The calculated adsorption energies of sulfur mustard on the surface of the nanocages showed that the Al12N12, C12Si12 and Mg12O12 are useful for the adsorption of the sulfur mustard. The quantum theory atom in molecule (QTAIM) analysis was used to study the nature of interactions of sulfur mustard with the surface of the selected nanocages. Based on QTAIM analysis, the majority of interactions of sulfur and chlorine atoms of sulfur mustard with the surface of the considered nanocages are covalent and quasi covalent whereas the interactions of hydrogen atoms of sulfur mustard with the surface of the nanocages are generally non-covalent. The charge transfer between sulfur mustard and the nanocages as well as chemical quantum descriptors of complexes were calculated using natural bond orbital (NBO) method. The most electron charge transfers from the sulfur mustard to B12N12 nanocage where the S atom of sulfur mustard donor a chemical bond to B atom of the nanocage. The ability of the considered nanocages for detecting sulfur mustard was studied using time-dependent density function theory (TD-DFT) and density of state (DOS) diagram. It is found that the C24, Al12P12, Be12O12 and B12N12 nanocages are useful sensors for this chemical agent.

Diffusion of alkali metal atoms (Li, Na, K) on aluminum nitride and boron nitride nanocages; a density functional theory study

Density functional calculations have been performed to study the diffusion behavior of various alkali metal atoms on the surface of (AlN)12 and (BN)12 nanocages. Alkali metal doped nanocages possess remarkable nonlinear optical response. A number of studies in the literature discuss the structural, electronic, nonlinear and sensor applications of pure and doped X12Y12 nanocages. Alkali metal atom doping at different adsorption sites is reported; however, the information regarding the interconversion barriers for the diffusion of alkali metals on these structures is still unknown. In this study, the barriers for the diffusion of alkali metal atoms (Li, Na, K) on these nanocages are studied at ωB97XD method. The barriers are obtained by scanning potential energy surface along the movement of alkali metals through the nanocage. The barriers for the diffusion of lithium atom on AlN nanocage are found to be higher than BN nanocage. The highest interconversion barrier calculated is 48.77kcalmol−1 for b66 to r6 movement of lithium atom on AlN nanocage. The lowest migration barrier is observed for sodium movement from r6 to b66 in AlN nanocage.

Interaction of B12N1 and Al12N12 Nano-Cages with Amino Acids: A Density Functional Theory Study

In this study, the adsorption of histidine and tyrosine molecules on Al12N12 and B12N12 nanocages has been investigated for the development of a new sensor for these amino acids. This was done using the density functional calculations of the geometry, frequency, Fukui indices, and the density of state analysis. The electronic properties of the Al12N12 and B12N12 nanocages make them sensitive to the presence of amino acid molecules, affecting the energy gap of the nanocages after the adsorption process. Based on the calculated results, the Al12N12 and B12N12 nanocages are expected to be a promising and novel sensor for histidine and tyrosine molecules. Basis set super position error (BSSE) in the density functional theory calculation was applied to investigate the interaction between the histidine and tyrosine molecules with the Al12N12 and B12N12 nanocages. The interaction energies demonstrate that the histidine and tyrosine molecules are adsorbed on these nanocages through an exothermic process. It is observed that the Al12N12 nanocage is more sensitive to the histidine and tyrosine molecules than the B12N12 nanocage to serve as a biochemical sensor.

DFT study on the adsorption behavior and electronic response of AlN nanotube and nanocage toward toxic halothane gas

We have investigated the adsorption of a halothane molecule on the AlN nanotube, and nanocage using density functional theory calculations. We predicted that the halothane molecule tends to be physically adsorbed on the surface of AlN nanotube with adsorption energy (Ead) of −4.2 kcal/mol. The electronic properties of AlN nanotube are not affected by the halothane, and it is not a sensor. But the AlN nanocage is more reactive than the AlN nanotube because of its higher curvature. The halothane tends to be adsorbed on a hexagonal ring, an AlN bond, and a tetragonal ring of the AlN nanocage. The adsorption ability order is as follows: tetragonal ring (Ead = −14.7 kcal/mol) > AlN bond (Ead = −12.3 kcal/mol) > hexagonal ring (Ead = −10.1 kcal/mol). When a halothane molecule is adsorbed on the AlN nanocage, its electrical conductivity is increased, demonstrating that it can yield an electronic signal at the presence of this molecule, and can be employed in chemical sensors. The AlN nanocage benefits from a short recovery time of about 58 ms at room temperature.