Adsorption and sensor applications of C2N surface for G-series and mustard series chemical warfare agents

Yar, Muhammad; Ahsan, Faiza; Gulzar, Adnan; Ayub, Khurshid

doi:10.1016/j.micromeso.2021.110984

Cited by 25 publications

(13 citation statements)

References 69 publications

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“…The HOMO–LUMO energy gap (Eg) which have a significant influence on the chemical reactivity of the systems. It thus measures the extent of resistance to the change in the electron distribution of the studied systems 26 – 28 . As shown in Table 1 , a comparative study of the calculated HOMO–LUMO energy gap (Eg) of both bare and H-adsorbed systems was studied.…”

Section: Resultsmentioning

confidence: 99%

Electrocatalytic activity of metal encapsulated, doped, and engineered fullerene-based nanostructured materials towards hydrogen evolution reaction

Louis

Ikenyirimba

Unimuke

et al. 2022

Sci Rep

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The utilization of nanostructured materials as efficient catalyst for several processes has increased tremendously, and carbon-based nanostructured materials encompassing fullerene and its derivatives have been observed to possess enhanced catalytic activity when engineered with doping or decorated with metals, thus making them one of the most promising nanocage catalyst for hydrogen evolution reaction (HER) during electro-catalysis. Prompted by these, and the reported electrochemical, electronic and stability advantage, an attempt is put forward herein to inspect the metal encapsulated, doped, and decorated dependent HER activity of C 24 engineered nanostructured materials as effective electro-catalyst for HER. Density functional theory (DFT) calculations have been utilized to evaluate the catalytic hydrogen evolution reaction activity of four proposed bare systems: fullerene (C 24 ), calcium encapsulated fullerene (Ca enc C 24 ), nickel-doped calcium encapsulated fullerene (Ni dop Ca enc C 24 ), and silver decorated nickel-doped calcium encapsulated (Ag dec Ni dop Ca enc C 24 ) engineered nanostructured materials at the TPSSh/GenECP/6-311+G(d,p)/LanL2DZ level of theory. The obtained results divulged that, a potential decrease in energy gap (E gap ) occurred in the bare systems, while a sparing increase was observed upon adsorption of hydrogen onto the surfaces, these surfaces where also observed to maintain the least E H–L gap while the Ag dec Ni dop Ca enc C 24 surface exhibited an increased electrocatalytic activity when compared to others. The results also showed that the electronic properties of the systems evinced a correspondent result with their electrochemical properties, the Ag-decorated surface also exhibited a proficient adsorption energy and Gibb’s free energy (ΔG H ) value. The engineered Ag-decorated and Ni-doped systems were found to possess both good surface stability and excellent electro-catalytic property for HER activities.

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Section: Resultsmentioning

confidence: 99%

Electrocatalytic activity of metal encapsulated, doped, and engineered fullerene-based nanostructured materials towards hydrogen evolution reaction

Louis

Ikenyirimba

Unimuke

et al. 2022

Sci Rep

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“…According to the divergence theorem, the density of net gradient flux is indicated by the Laplacian (∇ 2 ρ) sign. A positive sign of Laplacian (∇ 2 ρ > 0) indicates that the flux is leaving, whereas the negative sign (∇ 2 ρ < 0) shows that flux is entering in an infinitesimally small volume in the vicinity of the reference point [ 47 ]. Therefore, the sign of Laplacian indicates the accumulation or depletion of electron density at the reference point.…”

Section: Computational Methodologymentioning

confidence: 99%

“…Recently, 2D C 2 N surface has been investigated for the selective detection of NH 3 as an electrochemical sensor [ 43 , 46 ]. The presence of an electron-rich nitrogenated cavity makes the adsorption process facile; therefore, C 2 N surface is a promising candidate for adsorption and sensing applications [ 47 ].…”

Section: Introductionmentioning

confidence: 99%

“…In our previously reported studies on C 2 N surface, C 2 N showed high selectivity towards NH 3 (among studied toxic analytes; HF, PH 3 , HCN, NH 3 , and H 2 S), NM (N-mustard) (among studied analytes; GA, GB, GF, GD, NM, and SM) and NI 3 (among studied nitrogen halides; NBr 3 , NCl 3 , and NI 3 ) on conductivity basis. In summary, the C 2 N surface has remained selective towards analytes that exhibit S–H, N–H, or C–H bonds of a methyl group attached to a phosphorus or nitrogen group [ 40 , 43 , 47 , 48 ]. Additionally, C 2 N surface bears a well-defined activity that is better suited for the adsorption of V-type nerve agents.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Efficient Detection of Nerve Agents through Carbon Nitride Quantum Dots: A DFT Approach

et al. 2023

Self Cite

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V-series nerve agents are very lethal to health and cause the inactivation of acetylcholinesterase which leads to neuromuscular paralysis and, finally, death. Therefore, rapid detection and elimination of V-series nerve agents are very important. Herein, we have carried out a theoretical investigation of carbon nitride quantum dots (C2N) as an electrochemical sensor for the detection of V-series nerve agents, including VX, VS, VE, VG, and VM. Adsorption of V-series nerve agents on C2N quantum dots is explored at M05-2X/6-31++G(d,p) level of theory. The level of theory chosen is quite adequate in systems describing non-bonding interactions. The adsorption behavior of nerve agents is characterized by interaction energy, non-covalent interaction (NCI), Bader’s quantum theory of atoms in molecules (QTAIM), frontier molecular orbital (FMO), electron density difference (EDD), and charge transfer analysis. The computed adsorption energies of the studied complexes are in the range of −12.93 to −17.81 kcal/mol, which indicates the nerve agents are physiosorbed onto C2N surface through non-covalent interactions. The non-covalent interactions between V-series and C2N are confirmed through NCI and QTAIM analysis. EDD analysis is carried out to understand electron density shifting, which is further validated by natural bond orbital (NBO) analysis. FMO analysis is used to estimate the changes in energy gap of C2N on complexation through HOMO-LUMO energies. These findings suggest that C2N surface is highly selective toward VX, and it might be a promising candidate for the detection of V-series nerve agents.

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“…The quantum theory of atoms in molecules (QTAIM) provides comprehensive evidence about the existence, strength, and characteristics of different molecular interactions in various complexes [52][53][54]. Molecular graphs for all SO 3 -(H 2 O)n (n = 1-7) clusters are depicted in Fig.…”

Section: Nature Of Intermolecular Interactionmentioning

confidence: 99%

The structure, stability, thermochemistry, and bonding in SO3-(H2O)n (n = 1–7) clusters: a computational analysis

Suvitha¹,

Venkataramanan

Sahara

2022

Struct Chem

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The structure, stability, and intermolecular interactions in SO3-(H2O)n(n = 1 -7) clusters were investigated using density functional and wave functional methods. The putative global minimum shows the SO3molecule tends to be on the surface water clusters. The increase in the number of water molecules chalcogen bond distance between water molecules and SO3decreases, while the maximum number of water molecules coordinated to the SO3molecule remains at three. The calculated solvation energy increases with the increase in the number of water molecules and it does not saturate, which indicates that the addition of water molecules can add up to the existing water cluster network. The interaction energy between water molecules and SO3was less than the solvation energy conforming to the cluster forming of water molecules. The Gibbs free energy and entropy values decrease with the increase in cluster size, signifying the amount of water molecule decide the sequential hydration process. Thermochemistry data at various temperatures show that low-temperature regions found in the upper part of the troposphere favor hydration formation. Molecular electrostatic potentials (MESP) show reduced Vs,max value of π-hole on sulfur atom, and increased value on hydrogens of water molecules which results in the addition of water which leads to the sequential addition of water molecules to the water network. The quantum theory of atoms in molecules (QTAIM) shows the presence of S•••O, O•••H interactions between SO3and water molecules. Between water molecules O•••H, H-bonding interactions were observed, and in larger clusters, O•••O interaction was also noticed.QTAIM analysis shows the water-water HBs in these clusters are weak H-bond, while the SO3-water interaction can be classi ed as medium H-bonds which was further supported by the NCI and 2D RDG plots.

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Adsorption and sensor applications of C2N surface for G-series and mustard series chemical warfare agents

Cited by 25 publications

References 69 publications

Electrocatalytic activity of metal encapsulated, doped, and engineered fullerene-based nanostructured materials towards hydrogen evolution reaction

Electrocatalytic activity of metal encapsulated, doped, and engineered fullerene-based nanostructured materials towards hydrogen evolution reaction

Efficient Detection of Nerve Agents through Carbon Nitride Quantum Dots: A DFT Approach

The structure, stability, thermochemistry, and bonding in SO3-(H2O)n (n = 1–7) clusters: a computational analysis

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