Al12N12 Nanocage Research Articles

Advances in Selective Detection of Cadaverine by Electronic, Optical, and Work Function Sensors Based on Cu-Modified B12N12 and Al12N12 Nanocages: A Density Functional Theory (DFT) Study.

This work explores Cu-modified B12N12 and Al12N12 nanocages for cadaverine diamine (Cad) detection using advanced density functional theory (DFT) calculations. The study found that Cu modification altered the geometry of the nanocages, increased the dipole moment, reduced the energy gap, and enhanced the reactivity. While pristine B12N12 and Al12N12 were not sensitive to Cad, the modified Cu(b64)B12N12 and Cu(b66)Al12N12 nanocages showed significantly higher electronic sensitivity (Δgap = 39.8% and 35.6%, respectively), surpassing the literature data. However, molecular dynamics (MD) revealed that the Cu(b66)Al12N12 nanocage is not stable in the long term, since the nanocage changes configuration to Cu(b64)Al12N12, which is less sensitive and has an even longer recovery time for Cad sensing. Adsorption energy analysis (Eads) showed a strong interaction of Cad/nanocages, while charge analysis suggested that the nanocages act as Lewis acids, accepting electrons from Cad. UV-vis spectra confirmed that Cu(b64)B12N12 responds optically to the presence of Cad. Furthermore, Cu(b64)B12N12 showed greater sensitivity to Cad compared to NO, H2, H2S, CO, COCl2, N2O, N2 gases, or H2O, showing high selectivity to diamine against interfering gases or water, standing out as a promising material for environmental applications in electronic, optical or work function sensors for cadaverine detection, even in humid environments.

Understanding the adsorption performance of hetero-nanocages (C12-B6N6, C12-Al6N6, and B6N6-Al6N6) towards hydroxyurea anticancer drug: a comprehensive study using DFT.

Cancer is a paramount health challenge to global health, which forms tumors that can invade nearby tissues and spread to neighboring cells. Recently, nanotechnology has been used to control the growth of cancer, in which anticancer drugs are delivered to cancerous cells via nanoparticles without damaging healthy tissues. In this study, DFT investigations were carried out to examine the adsorption behavior of C24, B12N12, and Al12N12 nanocages as well as their heterostructures C12-B6N6, C12-Al6N6, and B6N6-Al6N6 towards the hydroxyurea (HU) anticancer drug. In this regard, adsorption energy, interaction distance between the drug and nanocages, charge transfer, energy gap, dipole moment, quantum molecular descriptors, work function, and COSMO surface analysis were analyzed to understand their adsorption performance. Findings demonstrate that the adsorption energies of two hetero-nanocages on their hexagonal (SH) and tetragonal (ST) sites are favorable for the drug delivery process. The computed adsorption energy of B6N6-Al6N6 of the ST/AlN site is 183.59 kJ mol-1, which is higher than that of the C12-Al6N6 nanocage, including minimum adsorption distances. Negative adsorption energy with low adsorption distances implies an attractive interaction between the drug and nanocages. During the interaction, a significant amount of charge is transferred between the drug and nanocages. Furthermore, for both complexes, larger dipole moments were observed in water media compared to gas media. From DOS spectra, prominent peaks were found in the Fermi level after adsorption of HU on the nanocages, implying the reduction of the energy gap. Noticeable overlaps between the PDOS spectra of the nanocages and HU's close contact atom demonstrate the formation of chemical bonds between two specific atoms. Therefore, it can be concluded that among the nanocages, C12-Al6N6 and B6N6-Al6N6 may be suitable carriers for HU drug.

Computational analysis of bare and alkali metal-encapsulated Al12N12 nanocages for enhanced removal of fluoroquinolone antibiotics from wastewater

Antibiotics, particularly fluoroquinolones, and their residues pose significant risks to both aquatic and human life, underscoring the need for effective removal strategies. While nanomaterials show promise in addressing this issue, the theoretical understanding of their interactions with antibiotics has been limited. In this context, we conducted DFT calculations to explore the interactions between fluoroquinolone antibiotics and the Al12N12 nanocage, aiming to provide valuable data for future experimental investigations. In the present research, the adsorption behavior of fluoroquinolone (FQ) antibiotics including ciprofloxacin (C17H18FN3O3), gemifloxacin (C18H20FN5O4), levofloxacin (C18H20FN3O4), moxifloxacin (C21H24FN3O4), delafloxacin (C18H12ClF3N4O4) and ofloxacin (C18H20FN3O4) onto the surface of the bare and metal-encapsulated Al12N12 (Li-Al12N12 and Na-Al12N12) nanocages are studied using dispersion corrected density functional theory (DFT-D) calculations. The primary purpose is to explore the potential application of these nanomaterials for efficient fluoroquinolone removal. The results indicate that the encapsulation of Li or Na inside Al12N12 nanocage enhances the adsorption of the FQs. The desorption process is also investigated in acidic medium, revealing that Li-Al12N12 and Na-Al12N12 cages emerge as superior candidate than the bare Al12N12 nanocage for controlled FQs removal applications. The Li-Al12N12 and Na-Al12N12 are introduced as promising candidates for fluoroquinolone removal in aqueous medium. This study might provide an innovative perspective for future investigations in the field of the drug pollution removal using aluminum nitride-based nanomaterials.

Investigation of the adsorption of miglitol anti-diabetic drug on the surface of X12Y12 (X = B, Al; Y = N, P) nanocages: A DFT and COSMO insights

A DFT investigation has been carried out to understand the adsorption nature of the miglitol (MT) anti-diabetic drug on the surface of B12N12, B12P12, Al12N12, and Al12P12 nanocages in the gas and water phase. MT drug is physically adsorbed on the surface of B12N12 and B12P12 while chemisorption is observed for Al12N12 and Al12P12 nanocages. Al12N12 shows the highest adsorption energy of −2.08 eV in gas and −1.96 eV in water media respectively. The electronic HOMO–LUMO energy gaps were extremely reduced by about 48.21 %, 41.67 %, 4.02 %, and 9.92 % in the gas phase after the adsorption of MT drug onto the surface of the studied nanocages respectively which implies the increase in electrical conductivity of these nanocages. Dipole moment and COSMO surface analysis forecasted that Al12N12 and Al12P12 show more solubility in water media. Therefore, all the studied nanocages are favorable drug carriers and among them, Al12N12 can be used as a promising nano-vehicle for MT drug.

A DFT study of eugenol adsorption onto pure and Si-doped Al12N12 and B12N12 fullerene-like nanocages

Density functional theory (DFT) methods have been employed in this work to study the adsorption behavior of eugenol (Eug) on the external surface of pure and Si-doped Al12N12 and B12N12 fullerene-like nanocages. All calculations were performed using the M062X-D3 functional combined with the 6-311 + G(d,p) basic sets. In order to probe the reliability of the DFT method, three other functionals (B3LYP-D3, CB3LYP-D3 and WB97XD) were employed and no significant difference was observed in the adsorption energy values of the most stable configurations (AEII and BEII). Also, the complexes are found to be stable in standard conditions in gas and aqueous phases, and the adsorption process is found to be exothermic and spontaneous. Interestingly, Si-doped nanomaterials (Si-AEII and Si-BEII) form the most stable adsorbent-adsorate molecular states (Eads = −90.07 and −61.42 kcal/mol respectively) in gas phase. Furthermore, Si-AEII and Si-BEII complexes exhibit the highest reactivity, characterized by the lowest values of the HOMO-LUMO energy gap (5.50 and 7.07 eV respectively). MEP map of the studied systems showed electron rich and electron deficient sites. Natural bond orbital analyses revealed that the interaction of Al12N12 with Eug is mainly due to the strong electron delocalization LP(2)O10 → LP*(2)Al47 (E(2) = 34 kcal/mol), whereas in Eug-B12N12 complex, it is mainly due to the electron delocalization LP(2)O10 → P*(4)B36 (E(2) = 96.53 kcal/mol). The QTAIM analysis revealed that Si–O and Al–C/B–C bonds linking eugenol to doped cages are attractive weak interactions and their nature have been confirmed via RDG/NCI analyses. Indeed, the present study revealed the suitability of Si-doped Al12N12 and B12N12 fullerene-like nanocages for the efficient drug delivery of eugenol.

Computational screening of single-atom catalysts supported on Al12N12 nanocage for nitrogen reduction reaction

The electrochemical nitrogen reduction reaction (NRR) on TM@Al12N12(TM=Sc∼Cu, Mo, Ru∼Pd) nanocages are investigated by density functional theory (DFT) study. TM@Al12N12(TM=Cr, Co, Ni, Ru, Mo, Rh) are evaluated as potential candidate using N2 adsorption (ΔG(*N2)), protonation reactions in first step (ΔG(*N2-*NNH)) and final step (ΔG(*NH2-*NH3)). Among all the screened deposition systems, the NRR performance shows an increase over the pure Al12N12 nanocage and the first hydrogenation step (*N2-*NNH) is the potential determining step. The electronic effect and charge transfer of the system are analyzed by the density of states (DOS) and natural bond orbital (NBO) charge. The electron density difference and the frontier orbitals analysis reveal that the screened deposition nanocages exhibit a significantly improved activation of N2 compared to the pure Al12N12 nanocage. Especially, the Ru@Al12N12 has excellent reactivity for NRR with the limiting potential of −0.80 V via distal pathway.

Theoretical study of hydrogen storage in Li-decorated Al12N12 clusters

The hydrogen storage capacity of Li-decorated Al12N12 clusters is investigated using density functional theory computations. The present results indicate that Li atoms are strongly attached on tops of N atoms of the Al12N12 nanocage, forming Al12N12Lim (m = 1, 2, 4, 8, 12) complexes. The binding energies of the Li atoms on the Al12N12 are in the range of 1.60–1.95 eV, which are larger than that among Li atoms. The clustering of Li atoms can be effectively prevented on the surface of the host. The charge transfer from Li atoms to the Al12N12 makes Li atoms positively charged. Each Li atom in the Li-decorated Al12N12 complexes can adsorb a maximum of 3 H2 molecules with the average adsorption energy of 0.09–0.12 eV/H2. The polarization interaction is responsible for the adsorption of H2 molecules to Li-decorated Al12N12 complexes. The fully coated Al12N12Li12 complex can hold up to 36 H2 molecules, and the corresponding gravimetric density of hydrogen is 11.2 wt%, far exceeding the ultimate target of 6.5 wt% of U. S. DOE.

Adsorption of drugs on B12N12 and Al12N12 nanocages.

The adsorption behavior of twelve drug molecules (5-fluorouracil, nitrosourea, pyrazinamide, sulfanilamide, ethionamide, 6-thioguanine, ciclopirox, 6-mercaptopurine, isoniazid, metformin, 4-aminopyridine, and cathinone) on B12N12 and Al12N12 nanocages was studied using density functional theory. In general, the drug molecules prefer to bind with the boron atom of the B12N12 nanocage and the aluminium atoms of the Al12N12 nanocage. However, a hydrogen atom is transferred from each of 5-fluorouracil, nitrosourea, 6-thioguanine, ciclopirox, and 6-mercaptopurine to the nitrogen atom of the Al12N12 nanocage. All the drug molecules are found to be chemisorbed on the B12N12 and Al12N12 nanocages. The adsorption energies of the drug/B12N12 system are linearly correlated with the molecular electrostatic potential minimum values of the drug molecules. The transfer of the hydrogen atom from the drug molecules to the nitrogen atom of the Al12N12 nanocage leads to relatively high adsorption energies. We observed significant changes in the reactivity parameters (e.g. electronic chemical potential) of the nanocages due to the chemisorption process. Overall, the QTAIM analysis indicates that the interactions between drug molecules and nanocages have a partial covalent character. Among the studied systems, the adsorption process was more spontaneous for the ciclopirox/Al12N12 system in water.

Adsorption of gases on B12N12 and Al12N12 nanocages

Density functional theory (DFT) was used to study the adsorption of twenty-four different gases on the B12N12 and Al12N12 nanocages.

A DFT and QTAIM insight into ethylene oxide adsorption on the surfaces of pure and metal-decorated inorganic fullerene-like nanoclusters

In this industrial era, the use of low-dimensional nanomaterials as gas sensors for environmental monitoring has received enormous interest. To develop an effective sensing method for ethylene oxide (EO), DFT computations are conducted using method ωB97X-D and B3LYP with 6-31G(d,p) basis set to evaluate the adsorption behavior of ethylene oxide gas on the surfaces of pristine, as well as Scandium and Titanium decorated B12N12, Al12N12, and Al12P12 nanocages. Several properties like structural, physical, and electronic are studied methodically to better understand the sensing behavior. Scandium-decorated aluminum phosphate and boron nitride nanocages were shown to perform better in terms of adsorption properties. The short recovery time observed in this study is beneficial for the repetitive use of the gas sensor. The Natural Bond Orbital and molecular electrostatic potential analysis demonstrated a substantial quantity of charge transfer from adsorbate to adsorbents. The bandgap alternation after adsorption shows an influence of adsorption on electronic properties. The interactions of adsorbate and adsorbents are further studied using the ultraviolet–visible predicted spectrum, and quantum theory of atoms in molecules all of which yielded promising findings.

Elucidating the adsorption of 2-Mercaptopyridine drug on the aluminum phosphide (Al12P12) nanocage: A DFT study

Adsorption amplitude of the aluminum phosphide (Al12P12) nanocage toward the 2-Mercaptopyridine (MCP) drug was herein monitored based on density functional theory (DFT) calculations. The adsorption process through MCP⋅⋅⋅Al12P12 complex in various configurations was elucidated by means of adsorption (Eads) energies. According to the energetic affirmations, the Al12P12 nanocage demonstrated potential versatility toward adsorbing the MCP drug within the investigated configurations and exhibited significant negative adsorption energies up to −27.71 kcal/mol. Upon the results of SAPT analysis, the electrostatic forces showed the highest contributions to the overall adsorption process with energetic values up to −74.36 kcal/mol. Concurrently, variations of molecular orbitals distribution along with alterations in the energy gap (Egap) and Fermi level (EFL) of the studied nanocage were denoted after adsorbing the MCP drug. The favorable impact of water solvent within the MCP⋅⋅⋅Al12P12 complexes was unveiled and confirmed by negative solvation energy (ΔEsolv) values up to −17.75 kcal/mol. According to thermodynamic parameters, the spontaneous and exothermic natures of the considered adsorption process were proclaimed by negative values of ΔG and ΔH parameters. Significant changes in the IR and Raman peaks, along with the appearance of new peaks, were noticed, confirming the occurrence of the targeted adsorption process. Furthermore, the adsorption features of the MCP drug on the Al12N12 nanocage were elucidated and compared to the Al12P12 analog. The obtained results demonstrated the higher preferability of Al12P12 nanocage than the Al12N12 candidate towards adsorbing the MCP drug without structural distortion.

Assessment of the adsorption mechanism of amantadine drug onto pristine, Si- and Ge-doped Al12N12, and Al12P12 nanocages: A comparative DFT study

In the current study, the adsorption characteristics of pristine and doped (Si and Ge)- Al12N12 (AlN) and Al12P12 (AlP) nanocages towards the amantadine (AM) drug have been investigated in the gas phase by employing density functional theory (DFT). The study outcomes indicated that the amantadine drug interacts with the hexagonal ring of AlN and AlP nanocages through its H atoms and –NH2 group. The values of the adsorption energies on the pristine nanocages vary from −2.31 to −31.55 kcal/mol in the vacuum environment. However, after swapping out one of the central Al atoms with a Si or Ge atom, the adsorption energy of the doped AlN and AlP significantly increases towards the AM drug. From a thermodynamic perspective, the adsorption process of AM drug over Al12N12 and Al12P12 nanocarriers had a spontaneous and exothermic nature. The crucial and essential characteristics of the atoms in molecule (AIM) analysis, the negative and positive amounts of the total electron energy density and Laplacian parameters, respectively, illustrate that the examination interactions are a partial covalent nature. Charge transfer occurs from the AM molecule to the AlN and AlP nanocages, according to the Natural Bond Orbital (NBO) analysis. Taken altogether, these findings propose that the doped AlN and AlP nanocarriers are efficient aspirants for the development of the AM drug delivery process.

Density functional theory study of the sensing of ozone gas molecules by using fullerene-like Group-III nitride nanostructures

Recently, nanostructure-based gas sensors have drawn huge attention in this industrial era for environmental monitoring. We have performed DFT computations using B3LYP functional with6–31G Gaussian basis set to study the interaction of O3 molecules with B12N12, Al12N12, Ga12N12, AlB11N12, and GaB11N12 nanocages. To explore the sensing behavior, we have investigated structural properties, thermodynamic properties, electronic properties, dipole moment, and NBO charge transfer. The quantum theory of atoms in molecules (QTAIM) analysis displays that the interaction of O3 molecules with group-III nitride nanocages is a closed shell (non-covalent) type. The total density of state (DOS) graph shows that after adsorption the HOMO-LUMO band gap reduces in the significant range i.e. adsorption has a noteworthy influence on electronic properties. Therefore, AlB11N12, GaB11N12, and Al12N12 could be very promising in the field of sensing O3 molecules.

A comparative study of Mannosylerythritol lipids (MELs) surfactant adsorption upon the Al12N12 and B12N12 nano-cages as potential candidates for detecting MELs

Aluminum nitride and boron nitride nanocages have recently been discovered. The properties of these compounds vary according to their size. In this paper, we study the adsorption of MELs on aluminum nitride and boron nitride nanocages in the solution phase using density functional theory. The results of adsorption energies indicate that during the adsorption on aluminum nanocages, ether oxygen atoms show stronger adsorption, while adsorption is stronger on boron nitride nanocage from the hydroxyl group oxygen. The results of thermodynamic calculations indicate that all adsorption positions of aluminum nitride are thermodynamically favorable. However, in the case of boron nitride, some positions are thermodynamically unfavorable. In terms of recovery time, borne nitride is not a good adsorbent because of very small recovery time. The aluminum nitride may be able to behave as a suitable sensor for the MELs in the solution phase. Nevertheless, boron nitride does not have this capability, since it does not significantly change the number of conducting electrons.

Investigating the X-aminopyridine (X = 2 and 3) molecules sensing by Al12N12 and B12N12 fullerene-like nanocages: DFT, QTAIM, RDG and TD-DFT insights

DeThe adsorption of 2-aminopyridine (2-AP) and 3-aminopyridine (3-AP) on the external surface of B12N12 and Al12N12 fullerene-like nanocages (FLNs) is probed herein via DFT/M06-2X/6-311G(d,p) level of theory. It came out from the study that all FLN@X-AP states investigated are spontaneously formed. Moreover, topological analysis demonstrated that the boron nitride FLN can strongly adsorbed the APs through B-N covalent interactions. A significant change in the HOMO-LUMO band gap of B12N12, with values of 22.01 and 32.71% have been obtained following the adsorption of 2-AP and 3-AP respectively. Accordingly, the conductivity of B12N12 is greatly enhanced by the adsorption of the APs. The above mentioned observations, combined with those found from the analysis of dipole moments and molecular electrostatic potential maps predict B12N12 to be more sensitive to the aminopyridines investigated than the Al12N12 FLN from the theoretical point of view. Communicated by Ramaswamy H. Sarma

First-principles investigation of Hydroxycarbamide anticancer drug delivery by X12N12 (X = B, Al, Ga) fullerene nanostructures: A DFT, NBO and QTAIM analysis

The group-III nitride fullerenes (B12N12, Al12N12 and Ga12N12) are noncytotoxic and chemically stabile for human and are the perfect carriers for the delivery of drugs. This present study has computed the the different properties to explore the interaction among Hydroxycarbamide (HU) and X12N12 (B12N12, Al12N12 and Ga12N12) nanocages using DFT method both in gas and water phase. Our investigation exhibits that Al12N12 and Ga12N12 can be smart drug carrier for the delivery of HU drug as confirmation from the adsorption study. The energy of adsorption of all the complexes shows chemisorption type adsorption, indicating the interaction between the HU and Al12N12 and Ga12N12. The change of Eg of our studied structures indicates the sensitivity of the nanocages towards HU drug molecule. Therefore, it is predicted that HU drug onto the Al12N12 and Ga12N12 nanocages might be good delivery vehicle which will be helpful to which will benefit from saving human.

Theoretical Study of Alkaline-Earth Metal (Be, Mg, and Ca)-Substituted Aluminum Nitride Nanocages With High Stability and Large Nonlinear Optical Responses.

By replacing one Al or N atom of aluminum nitride nanocage Al12N12 with an alkaline-earth metal atom, two series of compounds, namely, M@Al12N11 and M@Al11N12 (M = Be, Mg, and Ca), were constructed and investigated in theory. The substituted effect of alkaline-earth metal on the geometric structure and electronic properties of Al12N12 is studied in detail by density functional theory (DFT) methods. The calculated binding energies, HOMO–LUMO gaps, and VIE values of these compounds reveal that they possess high stability, though the NBO and HOMO analyses show that they are also excess electron compounds. Due to the existence of diffuse excess electrons, these alkaline-earth metal-substituted compounds exhibit larger first hyperpolarizabilities (β 0) than pure Al12N12 nanocage. In particular, these considered compounds exhibit satisfactory infrared (IR) (>1800 nm) and ultraviolet (UV) (˂ 250 nm) transparency. Therefore, these proposed excess electron compounds with high stability may be regarded as potential candidates for new UV and IR NLO molecules.

Superalkali (Li2F, Li3F) doped Al12N12 electrides with enhanced static, dynamic nonlinear optical responses and refractive indices

In the present work, superalkalis (Li2F and Li3F) doped Al12N12 nanocages have been designed and investigated theoretically to elucidate the correlations between geometric, electronic and nonlinear optical properties. All complexes (A-E) are stable inorganic electrides as indicated by their interaction energies (−52.97 to −87.58 kcal/mol). The decrease in HOMO-LUMO energy gaps (5.44–5.87 eV) has caused a remarkable increase in the nonlinear optical response of A-E complexes. The maximum values of first hyperpolarizability (1.20 × 104 a.u.) and second hyperpolarizability (1.65 × 107 a.u.) have been achieved for complex A. The highest dynamic hyperpolarizability coefficients including second harmonic generation (9.08 × 105 a.u.) and electro-optic Pockel's effect (9.56 × 105 a.u.) are obtained for complex A at 532 nm. The electric field-induced second harmonic generation (up to 3.52 × 108 a.u.) and dc-Kerr effect (up to 8.13 ×108 a.u.) along with a large quadratic nonlinear refractive index (up to 5.41 × 10−11 a.u.) of the designed electrides reflected their large NLO response.

Exploring the adsorption ability with sensitivity and reactivity of C12-B6N6, C12-Al6N6, and B6N6-Al6N6 heteronanocages towards the cisplatin drug: a DFT, AIM, and COSMO analysis.

The DFT study on the adsorption behaviour of the C24, B12N12, and Al12N12 nanocages and their heteronanocages towards the anticancer drug cisplatin (CP) was performed in gas and water media. Among the three pristine nanocages, Al12N12 exhibited high adsorption energy ranging from -1.98 to -1.63 eV in the gas phase and -1.47 to -1.39 eV in water media. However, their heterostructures C12-Al6N6 and B6N6-Al6N6 showed higher interaction energies (-2.22 eV and -2.14 eV for C12-Al6N6 and B6N6-Al6N6) with a significant amount of charge transfer. Noteworthy variations in electronic properties were confirmed by FMO analysis and DOS spectra analysis after the adsorption of the cisplatin drug on B12N12 and B6N6-Al6N6 nanocages. Furthermore, an analysis of quantum molecular descriptors unveiled salient decrement in global hardness and increments in electrophilicity index and global softness occurred after the adsorption of CP on B12N12 and B6N6-Al6N6. On the other hand, the above-mentioned fluctuations are not so noteworthy in the case of the adsorption of CP on Al12N12, C12-B6N6, and C12-Al6N6. Concededly, energy calculation, FMO analysis, ESP map, DOS spectra, quantum molecular descriptors, dipole moment, COSMO surface analysis, QTAIM analysis, and work function analysis predict that B12N12 and B6N6-Al6N6 nanocages exhibit high sensitivity towards CP drug molecules.

Mechanism of ethanol steam reforming on B12N12 and Al12N12 nano-cages: A theoretical study

Density function theory calculations were employed in this study to investigate the ethanol steam reforming mechanism on B12N12 and Al12N12 nano-cages. The ethanol steam reforming on B12N12 and Al12N12 nano-cages was explored by OH, CαH, CαH, and CC bonds scission and forming hydrogen. The catalytic activity of two nano-cages was also assessed to identify a suitable catalyst. The calculations showed that ethanol steam consists of two stages of ethanol oxidation and water-gas shift reaction to produce H2 and CO2. Moreover, OH bond scission was a key step in ethanol steam reforming, and the formation of CH4 and CO in ethanol oxidation was favored. According to the calculations, the Al12N12 nano-cage was a more suitable catalyst due to its lower energy barrier in ethanol oxidation and water-gas shift reactions. Hirshfield charge analysis showed that with increasing metal property, more charge is transferred from the surface of Al12N12 nano-cage to intermediate species. The results clearly showed the mechanism and understanding of the importance of hydroxyl groups in ethanol vapor modification in B12N12 and Al12N12 nanocages, which could be useful in catalyst design and H2 formation.