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Topological diagrams LOL (left) and ELF (right) topological diagrams from the interaction of Al12N12 (a and b), Al12P12 (c and d), B12N12 (e and f), and B12P12 (g and h) nanocages with putrescine molecule
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A theoretical study on the interactions between X12Y12 nanocages (Al12N12, Al12P12, B12N12, and B12P12) and putrescine molecule (Put) is presented, using density functional theory (DFT) B3LYP/6-31+G(d) methodology. Structural, energetic, and electronic variations were observed for putrescine molecules adsorbed in nanocages, and results showed that...
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Carbon nitride nanoporous lattices are nowadays among the most appealing two-dimensional (2D) nanomaterials for diverse cutting-edge technologies. In one of the recent advances, novel C–C bridged heptazine of C6N7 with a nanoporous structure has been fabricated. Based on the experimentally realized C6N7 lattice and by altering the linkage chemistry...
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... We also used the concept of RMSD (Root-mean-square deviation of atomic positions) to evaluate the changes in the structure of the cage caused by the interaction with the TM atom. The RMSD has been used to compare the structures of similar proteins and molecules and to assess how much one differs from the other [71]. The RMSD value provides us with information on the root ...
... The relaxed structure of B 12 N 12 has an electric dipole moment equal to zero, as shown in other theoretical studies [5,7,16,31,71]. The dipole moment values of the nanocages formed by functionalizing the cage with TM increase significantly, indicating a greater charge separation in the nanocage formed, caused by the presence of the metal. We observed that the systems formed with the metal positioned inside the B 12 N 12 cage (encapsulated), in general, have lower dipole values compared to the other forms of modification, except for the systems with Cu, the only metal with which the encapsulated system has a higher dipole value than the other configurations. ...
The present study explores the modification of B12N12 nanocages with first-row transition metals (3d TM atoms) in the configurations: doped (TMB11N12, B12N11TM), decorated (TM@b64, TM@b66) and encapsulated (TM@B12N12) by DFT-D3 method at B3LYP/6-31G (d,p) level of theory, revealing enhanced stability and reactivity in decorated systems. Spin multiplicity analysis revealed the most stable spin state for each nanocage, showing that decorated systems are more stable at high spin. During geometry optimization, structural rearrangements were observed, with Cr@B12N12 emerging as the most stable configuration of the series, exhibiting a strong metal/cage affinity. The DOS study showed that modification with TM significantly changes the electronic properties of the nanocage, revealing a reduction in the HOMO–LUMO gap, increased reactivity and offering valuable information for applications in sensing, catalysis and energy storage. The RMSD data show that, in encapsulated systems, the TM moves from the center of mass to establish more intense interactions with the cage, as seen in the bond order analysis and it is also observed that Zn weakly interacts with B12N12 at any of the studied configurations.
Graphical Abstract
... The potential for applying nanostructures as work function sensors related to current density. The variation in the electric current density (j) can be associated experimentally with the work function value (Φ) before and after the nanocage's interaction with the molecule to be detected, according to the equation below [55,56]: j = AT 2 e (−Φ∕kBT) , (3). Content courtesy of Springer Nature, terms of use apply. ...
Due to its distinctive properties and semiconducting characteristics, B12N12 has been the subject of many studies in the field of nanoscience, as it is a promising material for various applications, such as in electronics, catalysts, optoelectronic sensors and energy storage. In addition, the modification of B12N12 with transition metals (TM) increases its potential. Techniques such as charge decomposition analysis (CDA), UV–Vis spectroscopy, circular dichroism (CD), molecular dynamics (MD) and work function study (Φ) are applied in this work in order to investigate the dynamics of charge transfers, optical properties, chirality, electronic transitions and thermodynamic stability of pure and TM-modified B12N12. The calculations were developed at DFT-D3 and TD-DFT level with the B3LYP/6-31G(d,p) basis set. The CDA results showed that the charge transfer’s predominant direction is from the cage to the TM, and that, in general, the charge donation effect is greater than the back-donation. The UV–Vis spectra analysis shows that pure B12N12 absorbs in the IR region, while modification with TM shifts the absorption peaks to the visible region in some cases. We observed that the presence of TM caused deformations in the structure of some nanocages, which began to show chirality as well as CD and g-factor signals. Molecular dynamics revealed that B12N12 and most of the modified nanocages are stable systems, but some changes in configuration were observed. The work function analysis indicated specific nanocages’ potential in work function sensor applications.
Graphical Abstract
... Zhu et al. [18] report the fabrication of BN nanocages on a large scale by using a homemade B-N-O precursor. Recently, a lot of theoretical studies have been done on the interaction of the nanocages' surfaces with NO [22][23][24][25][26] and other molecules [27][28][29][30][31][32][33][34][35], revealing their potential for application as sensors. ...
... Other electronic properties were calculated for the nanocages, considering the greatest energy gap for those with doublet multiplicity. For instance, regarding Fermi Level, the B 12 N 12 results are in accordance with Silva et al. [33] (-4.59 eV) and Baei [59] (-4.27 eV). Table 2 shows that the Fermi Level increases for all Cu-modified nanocages: B 12 N 11 Cu (-3.83 eV), Cu@B 12 N 12 (-4.18 ...
This work studied the adsorption of nitrogen monoxide gas on Cu-modified B12N12 nanocage as a chemical sensor application. We performed quantum chemical calculations using density functional theory (DFT) at the B3LYP-D3/6-31G(d,p) level. Seven adsorption configurations of NO molecule on pristine B12N12 were tested to find the best interaction mode. The modification of B12N12 with copper resulted in five optimized structures: CuB11N12 and B12N11Cu (doped), Cu@b66 and Cu@b64 (decorated), and Cu@B12N12 (encapsulated). The quantum molecular dynamic analysis revealed that almost all isolated systems are stable. The results indicate that the NO gas weakly physisorbed on pure B12N12 nanocage, but the Cu-modifications improved adsorption performance. We also found that, over B12N12, the NO molecule prefers to adsorb on the O site rather than the N site. In addition, our findings showed that Cu@B12N12 has high electronic sensitivity (ΔEgap = 87.4%) and great conductometric potential (∆Φ = 48.9%) towards NO gas, when compared to the other modified systems. Regarding selective detection of NO gas among other gas molecules (CH4, N2O, SO2, CO2, H2, and NH3), the Cu@B12N12 system showed high selectivity for NO detection. Finally, the results for energy gap and work function demonstrated the capability of Cu@B12N12 as a conductometric and work function sensor material type for applications in the selective detection of NO gas.
Schematic representation of the detection of toxic gases onto Cu@B12N12 surface.
... In this regard, the development of sensors for the detection of CNCl could be viable and necessary to avoid potentially severe health problems in humans. Recently, theoretical studies have been conducted on the interaction of nanocage surfaces with other molecules, revealing their potential for application as chemical sensors [32][33][34][35][36][37][38][39][40]. ...
The development of sensors for hazardous gases based on metal-modified B12N12 nanocages has attracted the attention of researchers. In this theoretical study, the interactions of cyanogen chloride (CNCl) toxic gas with pristine and MB11N12 (M = Fe, Co, Ni, Cu, and Zn) nanocages were evaluated using density functional theory (DFT) at the B97-3c/6-31G(d,p) level for all of the studied systems. The results indicated a decrease in the energy band gap (Egap) after doping and that this effect was more pronounced for the CuB11N12 nanocage. The CNCl molecule was observed to chemically adsorb on all MB11N12 nanocages, but a stronger interaction occurred on the FeB11N12, and CoB11N12 nanocages (with high recovery times), with a moderate interaction occurring on the B12N12, NiB11N12, CuB11N12, and ZnB11N12 surfaces (with adequate recovery times and σ-donation being more effective than π-back-bonding). However, the NiB11N12 and CuB11N12 nanocages showed the highest electronic sensitivity (∆Egap) values (79.31% and 87.50%, respectively) for the adsorption of CNCl gas. Furthermore, based on performance analysis and comparison with previous results reported in the literature, it was found that NiB11N12 and CuB11N12 nanocages were superior sensor materials for application in the detection of CNCl toxic gas.
Graphical Abstract
... Nano cages such as AlN, AlP, BN, and BP [23] are significant for their properties regarding their adsorption capabilities and also because of their low electron attraction and large HOMO-LUMO gaps, as well as their exceptional physical and chemical properties [36]. X 12 Y 12 nano cages were found to be capable of sensing and acting on drug carrier for Sulfamide [37]. Because of their excellent electrical properties, chemical inertness, and thermal conduction, aluminum nitride (AlN)ceramics have recently attracted the attention of physicists, chemical engineers, and material scientists [38]. ...
The requirement of highly sensitive, selective and responsive sensor for biomolecules remains a subject of great interest and under the development. We aimed to explore new 0D materials such as C24, Al12N12 and Al12P12 fullerenes for glucose sensing using dispersion (D3) corrected Density functional theory calculation with B3LYP/6-31G(d,p) basis sets. Among these Al12P12 and Al12N12 show the strong chemisorption and charge is transferred from fullerenes to glucose while an optimal adsorption has been found for C24 with glucose in which charge is transferred from glucose to fullerene. Adsorption energy calculation, NBO analysis, Mulliken charge analysis, DOS calculation, RDG analysis, sensing response and UV spectra analysis have been performed to justify the interaction between glucose and C24 and their derivatives. All calculations favor our expected results and concludes that for Al12N12 and Al12P12 can be used for glucose isolation from mixture of the other biomolecules due to their high recovery time in range of 1019 and 1011 seconds while C24 as a detection purpose. Based on the Mulliken charge analysis it has been observed that charge have been transferred from Glucose to Al12N12 and Al12P12. On the effect of water solvent, it is observed that the nature of the adsorption for Al12N12 and Al12P12 towards glucose remains the same and it confirms their application as carrier.
... Despite these characteristics, some gases Further significant efforts have been made to synthesize these nanocages (BN) n [4,[24][25][26][27][28]. Recently, many theoretical studies have been carried out on the B 12 N 12 nanocage, revealing the potential of B 12 N 12 for application in chemical sensors [29][30][31]. ...
This systematic review presents an overview, from 2011 to 2022, of how pure B12N12 and B12N12-modified nanocages have been used to detect toxic gases from studies based on density functional theory (DFT). Searches were carried out in the ISI Web of Science, Science Direct, and Scopus databases to identify all studies related to B12N12 nanocages and, with the application of exclusion and inclusion criteria, to select articles involving theoretical studies of pure B12N12 and B12N12-modified nanocages as toxic gas sensors. In addition, from our analysis of these articles, we infer that a pure B12N12 nanocage can selectively detect O3, HNO, NO, CO, ClCN, and FCN gases. However, it cannot detect N2O and NH3. In contrast, metal-modified B12N12 nanocage can detect a wider range of gases such as CO, NH3, PH3, AsH3, SO2, O3, COCl2, NCCN, and ClCN. However, few studies have discussed the interference effects due to the presence of other gases in the atmosphere and/or the incorporation of different structural modifications (decorated, doped, and encapsulated) into the cage. Lastly, this systematic review will guide the development of new applications of nanocages in the selective detection of toxic gases.
Graphical Abstract
Schematic representation of the detection of different toxic gases on a B12N12 nanocage surface.
... Theoretical studies based on the density functional theory (DFT) have been conducted to understand the structural properties, and electronics of semiconductors, and show that the fullerene-like structure, with magic number n = 12, that is, X 12 Y 12 , was the most stable structure (Strout 2000;Wang et al. 2005Wang et al. , 2007. In recent years, many theoretical studies have been conducted on the interaction of the surfaces of nanocages with CO (Rostamoghli et al. 2018;Ammar et al. 2020;Vessally et al. 2017), and other molecules (Silva et al. 2021;Kaviani et al. 2021;Padash et al. 2020), demonstrating their potential for as application in conductometric sensors. Rostamoghli et al. (Rostamoghli et al. 2018) showed that the adsorption of CO on the surface of B 12 N 12 occurs preferentially by the carbon atom bound to the boron of the nanocages, with a difference in the adsorption energy of 0.06 eV, a decrease in the band gap (E gap ), and an increase in conductivity, according to the equation proposed by Li (Li 2006). ...
... The most stable optimized structures of the B 12 N 12 nanocage were formed from eight 6-membered (hexagon) rings and six 4-membered (tetragon) rings, such that the calculated electric dipole was zero (B3LYP and B97D functionals), in accordance with the results published in previous literature (Silva et al. 2021;Escobedo-Morales et al. 2019). In Fig. 1, the optimized structures for the nanocage are presented with EF = − 0.514 V/Å (Fig. 1a), EF = 0.0 V/Å (Fig. 1b), and EF = + 0.514 V/Å (Fig. 1c). ...
... We observed that the application of the external EF in the positive Y-axis caused a decrease in bond lengths of B 64 (1.486 to 1.474 Å) and B 66 (1.439 to 1.436 Å), while the application of the field in a negative sense caused an increase in the bond lengths of B 64 (1.486 to 1.499 Å) and B 66 (1.439 to 1.451 Å) to the B3LYP level of theory; the same trend was observed for the dates obtained with the B97D functional (see Fig. 1d, 1e, and 1f). The results (Fig. 1a) showed that for the B 12 N 12 nanocage, the B-N bond lengths were in agreement with those reported in previous studies (Silva et al. 2021;Baei 2013;Larki et al. 2019). ...
The interactions between carbon monoxide (CO) gas and boron nitride (B12N12) nanocage, in the absence and presence of an external electric field, were investigated using two DFT functionals (B3LYP and B97D), and 6-31G(d) basis set. An external electric field (EF) with its intensity ranging from − 0.514 to + 0.514 V/Å was applied to the B12N12 nanocage, CO molecule, and B12N12–CO complex. Negative EF gradually increased the B64 and B66 bond lengths, while positive EF decreased them in the B12N12 nanocage. Additionally, we obtained a parabolic relationship between band gap (Egap) and the external EF on the B12N12 cluster, with a maximum EF = 0 V/Å, for the B3LYP and B97D functionals. Negative EF enhanced the adsorption energy, while positive EF inhibited the adsorption energy for two functionals of the CO molecule on the B12N12 cluster. Moreover, increase in the EF resulted in a decrease in the dipole moment, Mulliken charge, and band gap energy, and an increase in the sensitivity for B3LYP (19.115 up to 46.738%) and B97D (30.097 up to 61.523%), from − 0.514 to + 0.514 V/Å. Our computational results demonstrated the capability of B12N12 as a sensor for potential applications in the detection of CO under an external electric field.
Graphical abstract
The efficacy of aluminium phosphide (Al12P12) nanocage toward sensing methanol (MeOH) and ethanol (EtOH) volatile organic compounds (VOCs) was herein thoroughly elucidated utilizing various density functional theory (DFT) computations. In this perspective, MeOH⋯ and EtOH⋯Al12P12 complexes were investigated within all plausible configurations. According to the energetic features, the EtOH⋯Al12P12 complexes exhibited larger negative values of adsorption and interaction energies with values up to −27.23 and −32.84 kcal mol⁻¹, respectively, in comparison to the MeOH⋯Al12P12 complexes. Based on the symmetry-adapted perturbation theory (SAPT) results, the electrostatic forces were pinpointed as the predominant component beyond the adsorption process within the preferable MeOH⋯ and EtOH⋯Al12P12 complexes. The findings of the noncovalent interaction (NCI) index and quantum theory of atoms in molecules (QTAIM) outlined the closed-shell nature of the interactions within the studied complexes. Substantial variations were found in the molecular orbitals distribution patterns of MeOH/EtOH molecules and Al12P12 nanocage, outlining the occurrence of the adsorption process within the complexes under investigation. Thermodynamic parameters were denoted with negative values, demonstrating the spontaneous exothermic nature of the most favorable complexes. New energy states were observed within the extracted density of states plots, confirming the impact of adsorbing MeOH and EtOH molecules on the electronic properties of the Al12P12 nanocage. The appearance of additional peaks in Infrared Radiation (IR) and Raman spectra revealed the apparent effect of the adsorption process on the features of the utilized sensor. The emerging results declared the potential uses of Al12P12 nanocage as a promising candidate for sensing VOCs, particularly MeOH and EtOH.
This work presents a theoretical study about the interaction between the carbon nanotubes (CNT), boron nitride nanotubes (BNNT) and gallium nitride nanotubes (GaNNT) with the pollutant diamines: cadaverine and putrescine,...
