AlN Nanosheets Research Articles

Density Functional Theory Study of AlN Nanosheets with Biphenylene Structure: Stability, Electronic, Thermoelectric, Mechanical, and Optical Properties

Density Functional Theory Study of AlN Nanosheets with Biphenylene Structure: Stability, Electronic, Thermoelectric, Mechanical, and Optical Properties

Theoretically evaluating transition metal activated two-dimensional bilayer tetragonal AlN nanosheet for high-performance HER/OER/ORR electrocatalysts

The search for catalysts with high activity in hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) processes has been an eminent avenue for mankind to acquire clean and renewable energy. To this end, more than a dozen transition metal (TM)-doped AlN systems have been investigated based on first-principles calculations in this study. Our calculation results show that Co@AlN-VAl can be operated as OER/ORR bifunctional catalysts with ηOER/ηORR of 0.5/0.33 V. Meanwhile, Pd@AlN-VAl exhibits the most excellent catalytic activity due to the very low HER overpotential (ηHER=0.009V). Furthermore, the origin of the high activity for Co@AlN-VAl in the OER/ORR process is illustrated by stating the d-band center and descriptor (φ). The Bader charge, the crystal orbital Hamiltonian population (COHP), spin density, and density of states (DOS) are analyzed to further recognize the intrinsic characteristics of this system. The study provides theoretical guidance for the application of AlN system in electrocatalysis and a window for new SACs.

A computational study on the mercaptopurine drug interaction with aluminum nitride nanostructures: analyzed by Marcus theory of electron-transfer

We analyzed the mercaptopurine adsorption on AlN nanostructures consisting of zero-dimensional nanoclusters, one-dimensional nanotubes, and two-dimensional nanosheets using calculations based on density functional theory (DFT). The adsorption energy, energy band gap, fluctuations in the energy band gap, charge transfers, and types of interactions that take place after mercaptopurine is adsorbed on the AlN nanostructures have all been calculated using DFT. The results show MP adsorption energies on AlN nanoparticles are −4.22, −5.95, and −8.70 eV. In this situation, MP molecules have been drawn to the surface due to the higher adsorption energies available on the AlN nanosheet (a process known as chemisorption). The Atoms in Molecules inquiry was conducted to learn more about and better comprehend the binding properties of the investigated AlN nanostructures utilizing mercaptopurine. Our findings indicate the mercaptopurine/AlN nanosheet bonding’s electrostatic properties. Additionally, the electrical conductivity of the AlN nanostructures increases whenever mercaptopurine is adsorbed on them. This shows that the AlN nanoparticles might function as chemical sensors and offer an electrical signal in mercaptopurine. The following is the order of sensitivity: AlN nanosheet > AlN nanotube > AlN nanocluster. The outcomes indicate that the nanosheet has the most potential for mercaptopurine detection among the AlN nanostructures. Communicated by Ramaswamy H. Sarma

Ab initio study of electronic and magnetic properties of zigzag and armchair AlN nanosheets

Ab initio study of electronic and magnetic properties of zigzag and armchair AlN nanosheets

Investigation of the adsorption behavior of the anti-cancer drug hydroxyurea on the graphene, BN, AlN, and GaN nanosheets and their doped structures via DFT and COSMO calculations.

To reduce the direct side effects of chemotherapy, researchers are trying to establish a new approach of a drug-delivery system using nanomaterials. In this study, we investigated graphene and its derivative nanomaterials for their favorable adsorption behavior with the anti-cancer drug hydroxyurea (HU) using DFT calculations. Initially, different pristine and doped graphene and its derivatives were taken into consideration as HU drug carriers. Among them, AlN, GaN, GaN-doped AlN, and AlN-doped GaN nanosheets exhibited favorable adsorption behavior with HU. The HU adsorbed on these four nanosheets with adsorption energies of -0.92, -0.75, -0.83, and -0.69 eV, transferring 0.16, 0.032, 0.108, and 0.230 e charges to the nanosheets, respectively, in air medium. In water solvent media, these four nanosheets interacted with HU by -0.56, -0.45, -0.58, and -0.56 eV by accepting a significant amount of charge of about 0.125, 0.128, 0.192, and 0.126 e from HU. The dipole moment and COSMO analysis also indicated that these nanosheets, except for GaN-doped AlN, show high asymmetricity and solubility in water solvent media due to the increased values of the dipole moment by two or three times after the adsorption of the HU drug. Quantum molecular descriptors also suggest that the sensitivity and reactivity of the nanosheets are enhanced during the interaction with HU. Therefore, these nanosheets can be used as anti-cancer drug carriers.

Bilayer tetragonal AlN nanosheets as potential cathodes for Li-O2 batteries.

Li-O2 batteries are considered promising electrochemical energy storage devices due to their high specific capacity and low cost. However, this technology currently suffers from two serious problems: low round-trip efficiency and slow reaction dynamics at the cathode. Solving these problems requires designing novel catalysis materials. In this study, a bilayer tetragonal AlN nanosheet as the catalyst is theoretically designed for the Li-O2 electrochemical system, and the discharge/charge process is simulated by a first-principles approach. It is found that the reaction path leading to Li4O2 is energetically more favored than the path to form a Li4O4 cluster on an AlN nanosheet. The theoretical open-circuit voltage for Li4O2 is 2.70 V, which is only 0.14 V lower than the formation of Li4O4. Notably, the discharge overpotential for forming Li4O2 on the AlN nanosheet is only 0.57 V, and the corresponding charge overpotential is as low as 0.21 V. A low charge/discharge overpotential can effectively solve the problems of low round-trip efficiency and slow reaction kinetics. The decomposition pathways of the final discharge product Li4O2 and the intermediate product Li2O2 are also investigated, and the decomposition barriers are 1.41 eV and 1.45 eV, respectively. Our work shows that bilayer tetragonal AlN nanosheets are promising catalysts for Li-O2 batteries.

Unravelling the adsorption performance of BN, AlN, GaN and InN 2D nanosheets towards the ciclopirox, 5-fluorouracil and nitrosourea for anticancer drug delivery motive: A DFT-D with QTAIM, PCM and COSMO investigations

In this work, the sensitivity and reactivity of graphene like 2D nanosheets such as BNNS, AlNNS, GaNNS and InNNS towards ciclopirox (CPX), 5-fluorouracil (5-FU) and nitrosourea (NU) anticancer drugs have been investigated by DFT calculations. The adsorption energies and charge transfer calculations predict that among the four nanosheets, GaNNS is more attractive towards the CPX and 5-FU drugs whereas InNNS show more absorptivity towards NU drug in both gas as well as water media. The obtained adsorption energies for CPX/GaNNS, 5-FU/GaNNS and NU/InNNS are −1.39, −0.84 and −0.82 eV respectively. Dipole moment and COSMO surface analysis predicted that AlNNS and GaNNS show more solubility in solvent media like water media. QTAIM analysis suggests that non-covalent interaction occurred in all complexes except 5-FU/AlNNS, CPX/GaNNS and 5-FU/GaNNS where partially covalent and partially electrostatic interaction occurs in the complexes. Therefore, among the four nanosheets GaNNS may be used as promising nanocarrier for CPX and 5-FU whereas InNNS for NU anticancer drug.

Ab Initio Study of Electronic and Magnetic Properties of Zigzag and Armchair Aln Nanosheets

Ab Initio Study of Electronic and Magnetic Properties of Zigzag and Armchair Aln Nanosheets

A DFT study on AlN nanotubes and nanosheets as anodes for Mg-ion batteries

The potential applications of ((n, 0), n = 4–8) zigzag AlN nanotubes (zAlNNTs), ((n, n), n = 4–6) armchair AlN nanotubes (aAlNNTs) and AlN nanosheets in Mg-ion batteries (MIBs) have been investigated by density functional theory calculations. Through the calculations of the adsorption energy, diffusion energy, diffusion coefficient, and theoretical voltage, we find that with the increasing diameter of the AlN nanotube (AlNNT), the adsorption energy for Mg shows a decreasing trend, while the adsorption energy for Mg2+ shows a contrary trend. Eventually this will cause the voltage to rise with the increasing diameter of the AlNNT. In addition, the diffusion energy barrier tends to decrease and diffusion coefficient becomes larger as the diameter of the AlNNT increases. The smallest diffusion energy barrier is only 0.054 eV and the corresponding maximum diffusion coefficient is 1.51 × 10−3 cm2/s. Therefore, large-diameter AlNNTs are suitable candidates for the anode materials of MIBs.

Au-decorated semiconducting AlN nanosheet as an electronic sensor for theophylline drug

ABSTRACT Density functional theory calculations based on the TPSS functional were performed to investigate the potential application of the pristine AlN nanosheet (AlNNS) as well as the Au-decorated AlNNS (Au@AlNNS) in the detection of the theophylline (TP) drug. We found that the pristine sheet weakly adsorbed the drug, and its sensing response was about 6.0. After the Au-decoration on the AlNNS, the TP drug was powerfully adsorbed onto the Au@AlNNS with the adsorption energy of −1.33 eV, and the sensing response increased to 689.2. The localised molecular orbital energy decomposition analysis illustrated that the electrostatic attraction is stronger than the covalent interaction after the TP adsorption onto the Au@AlNNS. Based on the partial density of state analysis, the TP drug created a new state through the HOMO–LUMO gap of Au@AlNNS, which significantly increased the electrical conductivity. A short recovery time of 2.51 s was attained for the TP desorption from the Au@AlNNS surface. The water solvent weakened the adsorption process and decreased the sensing response to 524.6. Based on the results, we suggested the Au@AlNNS as a biosensor for the TP drug recognition.

Poisonous Vapor Adsorption on Pure and Modified Aluminum Nitride Nanosheet for Environmental Safety: A DFT Exploration

Through Density Functional Theory (DFT), we have unveiled the atomic structures, adsorption characteristics and electronic structures of the poisonous and explosive vapor, m-dinitrobenzene (m-DNB), on pure, defective and various doped AlN nanosheets from a physical perspective. It is found that the adsorption energy, band gap change and sensitivity to the vapor are significantly increased through atomic-scale modification of the nanosheet. The AlN monolayer with Al-N divacancy has the largest adsorption energy and has potential to be utilized as adsorption or filtration materials for m-DNB vapor. The Si-doped AlN nanosheet possesses a much larger band gap change (−0.691 eV) than the pure nanosheet (−0.092 eV) after adsorption and has a moderate adsorption energy, which could be candidate material for explosive vapor sensing. This theoretical work is proposed to provide guidance and clue for experimentalists to develop more effective two-dimensional materials for environmental safety and sustainability.

Pt-decorated graphene-like AlN nanosheet as a biosensor for tioguanine drug: A computational study

Two-dimensional nanostructures attracted considerable attention as chemical sensors for different biological molecules. Here, DFT calculations were performed to probe the potential application of pristine AlN nanosheet (AlNNS) as well as Pt-decorated AlNNS (Pt@AlNNS) in recognition of thioguanine (TG) drug. The sensing response of AlNNS to the TG is very small (~11.1 at 298 K) due to a small adsorption energy (AE) of −0.18 eV. The Pt atom preferentially adsorbed above an Al-N bond, releasing the energy of 2.72 eV. We found that the TG powerfully adsorbed on the Pt@AlNNS with AE of −1.12 eV and the sensing response increased to 485.3 by the Pt decoration. The recovery time was attained to be 11.9 s for the TG desorption from the Pt@AlNNS surface. Consequently, the Pt@AlNNS can transform the presence of TG molecules into electrical signal, and it may potentially be applied as an electronic sensor for TG drug detection.

Novel self-assembled microstructures made from Dy doped AlN nanosheets: Formation mechanism, photoluminescence and magnetic properties

Novel self-assembled Dy doped AlN (AlN:Dy) microstructures derived from nanosheets (NSs) were prepared using an improved arc discharge method. The structure, morphology, optical and magnetic properties of AlN:Dy microstructures were characterized by XRD, XPS, FESEM, HRTEM, PL and VSM studies. The electrostatic interactions of NSs arising from Dy3+ doping into AlN and electric field attraction created by arc discharge, are responsible for the formation of self-assembled AlN:Dy microstructures. The AlN:Dy microstructures exhibited an intensive white emission and room temperature ferromagnetism. This work not only demonstrates an effectivestrategy to assemble complex architectures, but also provides a new opportunity to design multifunctional materials, throughdoped wide band semiconductor.

Application of hexa‐peri‐hexabenzocoronene nanographene and its B, N, and Bn doped forms in Na-ion batteries: A density functional theory study

Although Li-ion batteries are widely used for different purposes, they suffer from safety problems, high cost, and short lifetime. Because of low cost, wide availability, and nontoxicity of sodium, Na-ion batteries (NIB) can be good alternative to the useful Li-ion batteries in the near future. Applying density functional density theory calculations, we investigated the potential application of the recently synthesized hexa‐peri‐hexabenzocoronene nanographene (HBC) and its B, N, and BN doped forms in the anode of NIBs. We found that doping the electron rich N atom in the structure of HBC makes it more suitable for application in the NIBs, while B-doping significantly reduces the cell voltage. We found that the value of cell voltage generated by the studied nanostructures in the NIBs has the following order: N-HBC (~ 1.87) > HBC (~ 1.41) > BN-HBC (~ 1.29) >> B-HBC (~ −0.53 eV). Our results indicate that the N-HBC nanographene generates the larger cell voltage compared to the graphene, BN, SiC, and AlN nanosheets.

AlN nanotubes and nanosheets as anode material for K-ion batteries: DFT studies

We explored the possible application of (5,0), (6,0), (7,0), (8,0) and (9,0) zigzag AlN nanotubes and an AlN nanosheet in the K-ion batteries (KIBs) using B3LYP-gCP-D3/6-31G* model chemistry. In the case of (5,0) tube, the K and K+ adsorption energies, maximum energy barrier for K+ migration, ion diffusion coefficient, and cell voltage are calculated to be −1.22 and −0.32 eV, 0.36 eV, 8.58×10−8 cm2/s, and 0.90 V, respectively. We found that dispersion term (D3) has much more significant effect on the K/K+ adsorption energies compared to the basis set superposition error (gCP). Reducing the AlN nanostructure curvature, the K atom interaction significantly weakens while the K+ interaction is slightly affected. As a result, the cell voltage increases by decreasing the AlN curvature, and reached to 1.11 V in the AlN sheet. The AlN nanostructures with lower curvature may be plausible candidates for application in the anode of KIBs.

Magnetic phase stability of transition metals doped (4,4) AlN nanosheet

Magnetic phase stability in transition metals doped (4,4) armchair AlN nanosheet were studied using first principle calculations for three different configurations and two magnetic states. Energy differences between ferromagnetic (FM) and antiferromagnetic (AFM) state suggest that the preferable magnetic state for the AlN nanosheet doped with a pair of Fe and Co atoms independent from doping site is AFM, while it is FM for Ni and Mn impurities. For the rest transition metals (Ti, V, Cr, and Cu) doped AlN nanosheet, magnetic state alters as the transition metals configuration varies. In order to identify the most stable configuration, the formation energy is calculated for all compounds. The results obtained from formation energy calculations revealed that the most stable configuration for a pair of (V, Mn, Fe, Co, and Cu) atoms doped AlN nanosheet is the configuration of I, while for Cr and Ni is the configuration of III. AlN nanosheets doped with (Ti, V, Fe, and Ni) atoms are more stable than nanosheets doped with Cr, Mn and Cu.

Interaction of nitrotyrosine with aluminum nitride nanostructures: A density functional approach

Abstract We investigated the adsorption of nitrotyrosine on the AlN nanostructures including zero-dimensional nanocluster, one-dimensional nanotube, and two-dimensional nanosheet using density functional theory calculations. Density functional theory calculations were performed for calculation of adsorption energy, energy band gap, changes in the energy band gap, charge transfers, and nature of interactions; upon adsorption of nitrotyrosine on the AlN nanostructures. In order to go further and gain insight into the binding features of considered AlN nanostructures with nitrotyrosine, the Atoms in Molecules analysis was performed. Our results determine the electrostatic features of the nitrotyrosine/AlN nanosheet bonding. Also, when the nitrotyrosine is adsorbed on the AlN nanostructures, their electrical conductivity is increased, revealing that the AlN nanomaterials can yield an electronic signal at the presence of this modified amino acid and can be utilized as chemical sensors. The order of sensitivity is as follows: AlN nanosheet > AlN nanotube > AlN nanocluster. Our results show that among the AlN nanostructures, the AlN nanosheet may be a promising candidate for detection of nitrotyrosine.

Enhanced thermal conductivity of cellulose nanofibril/aluminum nitride hybrid films by surface modification of aluminum nitride

In this work, γ-aminopropyltriethoxysilane treated aluminum nitride nanosheets (TAlN) were blended with cellulose nanofibrils (CNFs), and a novel nano-flexible composite film was prepared by vacuum filtration. The interactions between the CNFs and TAlN were studied, and the effect of the amount of the added TAlN on the properties of the composites was discussed. Due to the function of silane, the dispersibility of the AlN nanosheets in the CNF substrate is improved and resulting in the formation of covalent bonds between them. The silane treatment reduces the phonon scattering between the AlN and CNF substrate interfaces; thus, the composite film exhibits excellent thermal conductivity. The in-plane thermal conductivity of the composite film reaches 5.11 W/mK when the amount of TAlN added is 25 wt%. The high thermal conductivity composite film material can realize thermal management for flexible energy storage electronic products; thus, effectively promoting the development of green flexible electronic devices.

Electronic and optical properties of V doped AlN nanosheet: DFT calculations

Electronic and optical properties of pure and V-doped AlN nanosheet have been investigated using density functional theory, and the dielectric tensor is calculated using the random phase approximation (RPA). The results of structural calculations show that the V atoms tend to replace instead of aluminum atoms with the lowest formation energy. In addition, study of the electronic properties shows that pure AlN nanosheet is a p-type semiconductor that by increasing one V atom, it possesses the metallic properties and magnetic moment becomes Zero. Moreover, by replacing two V atoms, the half-metallic behavior with 100% spin polarization can be found, and each supercell gains a net magnetic moment of 3.99 µB. Optical properties like the dielectric function, the energy loss function, the absorption coefficients, the refractive index are calculated for both parallel and perpendicular electric field polarizations, and the results show that the optical spectra are anisotropic.

Potential application of AlN nanostructures in sodium ion batteries: a DFT study

ABSTRACTNa-ion batteries (NIBs) appear to be a replacement for Li-ion batteries due to the nontoxicity, low cost and wide availability of sodium. Here, we explored the Na and Na+ adsorptions on the AlN nanocluster, nanotube and nanosheet to study their potential application as an anode in NIBs, using density functional theory calculations. Based on our results, we can infer that both atomic and cationic sodium are preferentially adsorbed on a hexagon of the AlN nanostructures so that the Na+ adsorption is very stronger than Na adsorption. By decreasing the surface curvature, the Na and Na+ adsorptions are weakened and strengthened, respectively, and the cell voltage is increased as follows: Nanosheet (∼1.48 V) > Nanotube (∼1.06 V) > Nanocluster (∼0.86 V). The calculated value for carbon nanotube (from literature) is about 1.45 V based on the same method. The charge separation in Al–N bonds of nanostructures has the main role in the value of cell voltage. It was predicted that by decreasing the curvature, the charge separation is increased because of decreasing the length of Al–N bonds. Based on the results, we can conclude that AlN nanosheet may be a likely applicant in NIB anode, compared to the AlN nanotube and nanocluster.