Increase In Adsorption Energy Research Articles

First-principles study of the effect of oxygen vacancy and iridium doping on formaldehyde adsorption on the La2O3(001) surface.

Formaldehyde adsorption on intrinsic La2O3 surface, four-fold coordinated oxygen vacancy (VO4c), six-fold coordinated oxygen vacancy (VO6c), and iridium-doped La2O3(001) surface was studied by the first-principles method. The results show that formaldehyde adsorption on the Ir-doped La2O3(001) surface with VO6c is the strongest because of the directional movement of electrons caused by the interaction of the Ir-5d orbitals and internal oxygen vacancy, wherein the adsorption energy is 3.23 eV. This model showed a significant increase in adsorption energy, indicating that Ir doping improves the formaldehyde adsorption capacity of the La2O3(001) surface. The energy band analysis shows that iridium doping introduces impurity energy levels into the intrinsic La2O3 energy band, which enhances the interaction between the La2O3(001) surface and formaldehyde molecules. Density of state analysis indicated that the adsorption of formaldehyde molecules on the La2O3(001) surface is mainly due to the interaction between the O-2p, C-2p orbitals of formaldehyde and the Ir-5d orbital of iridium atoms. Furthermore, the existence of VO4c and VO6c defects has no effect on the position and shape of the valence and conduction bands. The effects of oxygen vacancy and iridium doping on the optical properties mainly appeared in the low-energy infrared and visible regions, making the O-2p, C-2p orbitals of formaldehyde and the Ir-5d, O-2p orbitals of the La2O3(001) surface become hybridized near the Fermi level and the electronic transition from the valence band to conduction band more likely to occur. The La2O3 material can be used as an ideal photocatalytic material for formaldehyde degradation.

First-principles investigations of As-doped tetragonal boron nitride nanosheets for toxic gas sensing applications.

Pristine and arsenic-doped tetragonal boron nitride nanosheets (BNNS and As-BNNS) have been reported as potential candidates for toxic gas sensing applications. We have investigated the adsorption behavior of BNNS and As-BNNS for CO2, H2S, and SO3 gas molecules using first-principles density functional theory (DFT). Both BNNS and As-BNNS possess negative cohesive energies of -8.47 and -8.22 eV, respectively, which indicates that both sheets are energetically stable. Successful adsorption is inferred from the negative adsorption energy and structural deformation in the vicinity of the adsorbent and adsorbate. As-doping results in a significant increase in adsorption energies from -0.094, -0.175, and -0.462 eV to -2.748, -2.637, and 3.057 eV for CO2, H2S and SO3 gases, respectively. Due to gas adsorption, the electronic bandgap in As-BNNS varies by approximately 32% compared to a maximum of 24% in BNNS. A notable fluctuation in the energy gap and electrical conductivity is seen, with ambient temperature being the point of maximal sensitivity. For SO3, the maximum charge transfer during adsorption in BNNS and As-BNNS is determined to be 0.08|e| and 0.25|e|, respectively. Due to the interaction with gases, all structures exhibit an extremely high absorption coefficient on the order of 104 cm-1 with minimal peak shifting. Additionally, doping an As atom on BNNS' surface remarkably improved its ability to sense CO2, H2S, and SO3 gasses.

Gas Sensing Properties of Pd-Decorated GeSe Monolayer toward Formaldehyde and Benzene Molecules: A First-Principles Study.

In this study, the gas sensing properties of formaldehyde (HCHO) and benzene (C6H6) adsorbed on two-dimensional (2D) pristine GeSe and Pd-decorated GeSe (Pd-GeSe) monolayers are studied by using first-principles calculations. The adsorption energies, electronic properties, optical properties, sensitivity, and recovery time of the gas adsorption systems have been thoroughly investigated. It is found that the adsorption of C6H6 on two substrate surfaces and the adsorption of HCHO on pristine GeSe are examples of physical adsorption. However, after HCHO adsorption on the Pd-GeSe monolayer, the adsorption system exhibits an increased adsorption energy of -1.21 eV, which is more favorable compared with the other adsorption systems studied. Moreover, the electron localization function and charge transfer from Pd-GeSe to HCHO are significantly enhanced, indicating distinct chemical adsorption behavior. Furthermore, it demonstrates a larger band gap change rate of 18.8% and a significant enhancement of optical absorption upon the adsorption of HCHO on the Pd-GeSe monolayer. Additionally, the appropriate sensitivity and moderate recovery time for the adsorption of HCHO on the Pd-GeSe surface indicate that the Pd-GeSe monolayer possesses an outstanding sensing capability for HCHO gas.

Unraveling the sorption mechanisms of ciprofloxacin on the surface of zeolite 4A (001) in aqueous medium by DFT and MC approaches

The adsorption mechanism of ciprofloxacin (CIP) and its ionic form were investigated using density functional theory (DFT) and molecular dynamics (MD), with the goal of forecasting their adsorption behavior in terms of gap energy, global reactivity descriptors, Fukui functions, adsorption energies, and density of state on the surface of zeolite 4A (001). Quantum chemical parameters related to the adsorption process were calculated, as well as the overall reactivity. According to DFT calculations, the zwetterionic form CIP± are the most stable and reactive and have a greater power of electron transfer compared to the other species. Under aqueous conditions, zeolite can adsorb ciprofloxacin (CIP) and its ionic forms, as revealed by molecular dynamics simulation. Ciprofloxacin in the zwitterionic form (CIP±) were more efficiently adsorbed to the surface of zeolite 4A (001) than the cationic (CIP+), anionic (CIP−), and neutral(CIP) forms; through the evaluation of adsorption energy, probability distribution, interaction, and density of state. The results also demonstrated that the compounds studied were adsorbed via the process of chemical bonding, which was confirmed by the negative values of the interaction energy. Furthermore, the negative adsorption energy values suggest a significant adsorption of all compounds, with electrostatic interactions (physisorption), diffusion into the pores, and n-π bonds (chemisorption) on the zeolite surface. The increase in adsorption energies and the proximity of the molecules studied to the zeolite surface indicate the predominance of chemisorption, and the adsorption of ciprofloxacin was found to be an exothermic and spontaneous process. Molecular dynamics (MD) modeling was in agreement with the DFT results.

Optimizing the Local Charge of Graphene via Iron Doping to Promote the Adsorption of Formaldehyde Molecules—A Density Functional Theory Study

Formaldehyde is a colorless, pungent, and highly volatile toxic gas known for its detrimental effects on the brain, respiratory, and nervous systems. The adsorption method emerges as an effective approach for detecting and mitigating formaldehyde gas, with the adsorption material serving as its core component. Graphene, a two-dimensional nanomaterial with remarkable properties, exhibits enhanced adsorption capabilities when subjected to metal doping, which alters its local geometric and charge characteristics. In this investigation, theoretical first-principles density functional technology was employed to optimize the efficiency of Fe-doped graphene in formaldehyde adsorption. The calculated adsorption bond length and energy were used to determine the type of adsorption. Then, the calculated Bader charge, density of states (partial density of states), and differential valence charge density distribution were used to analyze the electron transfer process before and after adsorption. Finally, the theoretical optical properties analysis result was applied to analyze the potential of Fe-doped graphene for formaldehyde detection. The findings indicated that Fe-doped graphene constitutes a viable and stable doping structure, accompanied by a notable shift in valence charge distribution around the doped iron atom. This altered charge distribution facilitated the chemical adsorption process, leading to reduced adsorption spacing and increased adsorption energy. Throughout the chemical adsorption process, there was evident charge transfer between carbon (formaldehyde) and iron atoms, as well as between oxygen (formaldehyde) and iron atoms. The formation of adsorption bonds primarily involved the p-orbital electrons of carbon and oxygen atoms, along with the p- and d-orbital electrons of iron atoms. Ultimately, the Fe-doped graphene material exhibited promising applications in the realm of formaldehyde molecular detection, marked by significant theoretical disparities in optical properties before and after the adsorption process.

Adsorption of SO2 Molecule on Pristine, N, Ga-Doped and -Ga-N- co-Doped Graphene: A DFT Study

SO2 (sulfur dioxide) is a toxic substance emitted into the environment due to burning sulfur-containing fossil fuels in cars, factories, power plants, and homes. This issue is of grave concern because of its negative effects on the environment and human health. Therefore, the search for a material capable of interacting to detect SO2 and the research on developing effective materials for gas detection holds significant importance in the realm of environmental and health applications. It is well known that one of the effective methods for predicting the structure and electronic properties of systems capable of interacting with a molecule is a method based on quantum mechanical approaches. In this work, the DFT (Density Functional Theory) program DMol3 in Materials Studio was used to study the interactions between the SO2 molecule and four systems. The adsorption energy, bond lengths, bond angle, charge transfer, and density of states of SO2 molecule on pristine graphene, N-doped graphene, Ga-doped graphene, and -Ga-N- co-doped graphene were investigated using DFT calculations. The obtained data indicate that the bonding between the SO2 molecule and pristine graphene is relatively weak, with a binding energy of −0.32 eV and a bond length of 3.06 Å, indicating physical adsorption. Next, the adsorption of the molecule on an N-doped graphene system was considered. The adsorption of SO2 molecules on N-doped graphene is negligible; generally, the interaction of SO2 molecules with this system does not significantly change the electronic properties. However, the adsorption energy of the gas molecule on Ga-doped graphene relative to pristine graphene increased significantly. The evidence of chemisorption is increased adsorption energy and decreased adsorption distance between SO2 and Ga-doped graphene. In addition, our results show that introducing -Ga-N- co-dopants of an “ortho” configuration into pristine graphene significantly affects the adsorption between the gas molecule and graphene. Thus, this approach is significantly practical in the adsorption of SO2 molecules.

F-doped carbon derived from asphalt by mechanochemical approach: More effective toward selective CO2 capture

Porous carbon materials are a preferred choice for CO2 capture and separation owing to unique physical and chemical properties. Here, mechanochemical synthesis of porous carbon (high surface area, up to 1188 m2g−1) and in situ fluorine doping have been accomplished with asphalt as carbon source and Teflon (PTFE) as porogen and fluorine-doped precursors. Ball milling treatment are indispensable for the subsequent carbonization process of asphalt-PTFE mixture. The particle mixing and surface activation in the solid state are promoted by the input of mechanical energy and reaction mixtures are exposed to mechanical force impact. Meanwhile, the micropores and polar functional groups rich in the as-prepared carbon materials both conduce to higher CO2 capture and increase in adsorption energy based on DFT calculation. As evidence, the CO2 uptake capacity reached to 4.1 mmol g−1 for F-C-30# at 273 K, 1 bar. The CO2/N2 selectivity could reach up to 54 under ambient conditions, thereby reflecting a highly competitive CO2-adsorption capacity.

Cation Defect-Engineered Boost Fast Kinetics of Two-Dimensional Topological Bi2 Se3 Cathode for High-Performance Aqueous Zn-Ion Batteries.

The challenge with aqueous zinc-ion batteries (ZIBs) lies in finding suitable cathode materials that can provide high capacity and fast kinetics. Herein, two-dimensional topological Bi2 Se3 with acceptable Bi-vacancies for ZIBs cathode (Cu-Bi2-x Se3 ) is constructed through one-step hydrothermal process accompanied by Cu heteroatom introduction. The cation-deficient Cu-Bi2-x Se3 nanosheets (≈4nm) bring improved conductivity from large surface topological metal states contribution and enhanced bulk conductivity. Besides, the increased adsorption energy and reduced Zn2+ migration barrier demonstrated by density-functional theory (DFT) calculations illustrate the decreased Coulombic ion-lattice repulsion of Cu-Bi2-x Se3 . Therefore, Cu-Bi2-x Se3 exhibits both enhanced ion and electron transport capability, leading to more carrier reversible insertion proved by in situ synchrotron X-ray diffraction (SXRD). These features endow Cu-Bi2-x Se3 with sufficient specific capacity (320mAhg-1 at 0.1Ag-1 ), high-rate performance (97mAhg-1 at 10Ag-1 ), and reliable cycling stability (70mAhg-1 at 10Ag-1 after 4000 cycles). Furthermore, quasi-solid-state fiber-shaped ZIBs employing the Cu-Bi2-x Se3 cathode demonstrate respectable performance and superior flexibility even under high mass loading. This work implements a conceptually innovative strategy represented by cation defect design in topological insulator cathode for achieving high-performance battery electrochemistry.

Structure of bound water layer on montmorillonite surface: The role of trans- and cis- vacant sites

Bound water on the surface of clay minerals determines the nature of a wide class of phenomena, from the diffusion of interlayer cations to synthesizing prebiotic macromolecules during the early Earth. However, the nature of forming the bound water layer's spatial structure and properties has yet to be fully investigated. Many factors, including peculiarities of structural charge distribution, surface adsorption centers, and OH-groups of the octahedral sheet of the clay minerals, can affect it in natural clays. In this work the role of hydroxyl ligands and isomorphic substitutions of the octahedral sheet in trans- and cis- vacant sites in the formation of the bound water layer structure on the basal surface of montmorillonite was studied by the Density Functional Theory. It was found out that in the case of single isomorphic substitution in the octahedral sheet OH-groups in the cis-vacant sites provide higher adsorption energy of water molecules on the basal surface as compared to OH-groups in the trans-vacant sites. The double isomorphic substitution in the octahedral sheet creates a mutual enhancement effect due to the difference in the structural arrangement of the OH-groups. This leads to an increase in the interaction with adsorbed water molecules. The maximum increase in adsorption energy is observed for the case with isomorphic substitutions of Mg-cis and Fe-trans in the octahedral sheet. The results of the theoretical study contribute to explaining the experimental data available in the literature.

First-principles study of beryllium substituted borophene as an anode material for Li/Na-ion batteries

In this work, we predict the effects of beryllium (Be) doping on β12 borophene as an electrode material for lithium-ion batteries (LIBs) and sodium-ion batteries (NIBs) by using first principles methods. The optimized Li and Na adsorption sites are identified, and we found that Be doping enhances a single Li/Na ion adsorption on β12 borophene with increased adsorption energy (−2.174/−1.765 eV for Li/Na). Before to and following adsorption of Li/Na, the electrical conductivity of Be-doped borophene was revealed by the finite density of states at the Fermi level. Be-doped borophene provides adequate open circuit voltages (0.84/0.80 V for LIBs/NIBs). Besides these advantages, most remarkably, BeB19 has an extremely high theoretical specific capacity of 2869/2087 mA h g−1 for LIBs/NIBs which is several times higher than the other discovered 2D materials. Our results support that Be doping has a positive effect on β12 borophene and can be used to create anodes with excellent electrochemical properties for both LIBs and NIBs.

Achieving smartphone-based colorimetric assay for Hg2+ with a bimetallic site strategy based on Hg2+-triggered oxidase-like catalytic activity of NSC/Co6Ni3S8 nanocomposite

Modulation of the nanozyme's catalytic activity is crucial for its real applications in detecting target analytes. Herein, we fabricated the nanocomposite (NSC/Co6Ni3S8) of N, S co-doped carbon and Co6Ni3S8 by a facile sol-gel approach. Compared to NSC/Ni9S8, NSC/Co6Ni3S8 with bimetallic active sites displayed better enzyme-mimetic activity. This nanocomposite could catalyze O2 to form ·O2− and oxidize colorless 3, 3′, 5, 5′-tetramethylbenzidine (TMB) into blue oxTMB. The other two free radicals (h+ and ·OH) played minor roles during the catalytic reaction. Hg2+ could integrate with S2− to form HgS and the surface charges of O2 were transferred to Hg2+ to promote O2 adsorption. DFT theoretical calculations highlight that the main reasons for the enhancing effect of Hg2+ on color development results from electron transfer and increased adsorption energy of O2 molecules onto the surface of NSC/Co6Ni3S8. By employing the oxidase-like activity of NSC/Co6Ni3S8 and Hg2+-triggered promoting effect, a colorimetric sensing platform was established for Hg2+ assay with a linear range of 10–200 μg/L and detection limit of 3 μg/L. Through integration with a smartphone-based APP “Thing Identify” software, a visual colorimetric assay for Hg2+ was constructed with a detection limit of 5 μg/L. Compared to the data detected by the mercury vapor meter, the relative recoveries of 92.4–108.1% evidenced the higher accuracy of this smartphone-based visual detection. Overall, the NSC/Co6Ni3S8-based colorimetric assay is convenient, rapid, and visual, and can be applied for routine monitoring of Hg2+ in real-world waters under outdoor conditions.

First-principles study of graphene intercalation in h-BN based resistance random access memory

Graphene intercalation between metal electrode and resistance layers has attracted extensive experimental and theoretical research because of its capability to manipulate the electronic structure and properties of hexagonal boron nitride based resistance random access memory. Herein, the interface characteristic, adsorption and migration behavior of Ti on pristine and defective graphene intercalation have been systematically investigated by utilizing the density functional theory method, which could help accurately preset defects and regulate the permeation process. Analysis of the interfacial contact form showed that Ohmic-type contact occurs between intercalation and resistance layer interface due to the heavy doping effect caused by charge accumulation on the h-BN layer surface upon introduction of intercalation. Ti metal adsorption at hollow site on defective graphene containing grain boundary with double vacancies was more energetically favorable than that on pristine graphene without vacancy or with single vacancy, whereas the increase of adsorption energy caused by grain boundary defects that represented by pentagons and heptagons and double vacancies were very limited. Migration barrier calculations with defect distribution and vacancy indicated that the critical factor controlling ion penetration in the whole intercalation process is the presetting of single vacancy defect rather than the varying number of vacancies and the existence of grain boundary defect. This finding provides a new perspective aiding understanding and design of the defect-assisted graphene intercalation mechanism.

Dispersion-Corrected DFT-D4 Study of the Adsorption of Halobenzenes and 1,3,5-Trihalobenzenes on the Cu(111) Surface─Effect of Sigma Hole Properties.

Halogen bonds, characterized by directionality, tunability, hydrophobicity, and variable sizes, are ideal noncovalent interactions to design and control the formation of self-assembled nanostructures. The specific self-assembly cases formed by the halogen-bonding interaction have been well studied by scanning tunneling microscopy (STM) experiments and density functional theory (DFT) calculations. However, there is a lack of systematic theoretical adsorption studies on halogenated molecules. In this work, the adsorption of halobenzenes and 1,3,5-trihalobenzenes on the Cu(111) surface was examined by dispersion-corrected DFT methods. The adsorption geometries, noncovalent molecule-surface interactions, electronic densities, and electrostatic potential maps were examined for their most stable adsorption sites using the DFT-D4 method. Our calculations revealed that the iodo compounds favor a different adsorption geometry from aryl chlorides and bromides. Down the halogen group (Cl to I), the adsorption energy increases and the distance between the halogen atom and Cu surface decreases, which indicates stronger molecule-surface interactions. This is supported by the changes in the density of states upon adsorption. Noncovalent interaction analysis was also employed to further understand the nature and relative strength of the molecule-surface interactions. Electrostatic potential maps revealed that the positive character of the halogen sigma hole becomes stronger upon adsorption. Thus, surface adsorption of the halogenated molecule will enhance the formation of intermolecular halogen bonds. The present theoretical findings are expected to contribute toward a more comprehensive understanding of halogen bonding on the Cu(111) surface.

Regulating electron distribution of P2-type layered oxide cathodes for practical sodium-ion batteries

For transition metal oxide materials, high Ni content is an effective method to obtain a high specific capacity. However, the theoretical capacity is determined due to the certain amount of variable charges of transition metal ions. The increased capacity in specific voltage window may attribute to the easier transport of alkali ions, instead of more active elements. Borrowing the theory of Ni-rich materials in LIB, excess Ni elements were added into P2-type layered oxide material to form the Jahn-Teller active Ni3+ ions. About 25%-61% Ni3+ ions can effectively promote de-/intercalation of Na+ ions due to the decreased diffusion energy barrier and increased adsorption energy of Na+. The preferred “Ni-rich” material Na0.67Mn0.45Ni0.22Co0.33O2 (Ni-R1) shows a reversible specific capacity of 114 mA h g−1 in the voltage range of 2.0–4.25 V. In addition, it shows an excellent cycle stability, the capacity retention ration is 80% after 1000 cycles at a current density of 1 A g−1. The in-depth study proves that, Jahn-Teller active Ni3+ ions can effectively regulate the valence electron distribution of surrounding ions in synthesis stage. However, it will promote Jahn-Teller distortion when the Ni3+ content is increased to 74%, which makes the rate performance deteriorate dramatically. The present work provides a simple and efficient way to increase the capacity in suitable voltage range for application.

Using DFT to explore the sensitivity of WSe2/phosphorene heterostructure toward HCN

This study investigated the adsorption behavior of the HCN molecule on pristine and vacancy-defected (W and Se vacancies) and transition metal (TM; Sc, Ti, V, Cr, Mn, Fe, Co, Ni) -doped WSe2/phosphorene heterostructures through density-functional theory (DFT) calculations. As indicated by the results, the pristine and W-vacancy-defected WSe2/phosphorene structures exhibited weak adsorption capacity for HCN. Introducing Se vacancies enhanced the adsorption stability of HCN. Furthermore, combining TM impurities and Se vacancies decreased the adsorption distance, increased adsorption energy, and increased charge transfer, indicating a substantial improvement in the sensitivity of WSe2/phosphorene heterostructures to HCN. These findings suggest a potential new method for preparing gas sensors capable of detecting highly toxic hydrocyanic acid gas.

Defect-Engineering of 2D Dichalcogenide VSe2 to Enhance Ammonia Sensing: Acumens from DFT Calculations

Opportune sensing of ammonia (NH3) gas is industrially important for avoiding hazards. With the advent of nanostructured 2D materials, it is felt vital to miniaturize the detector architecture so as to attain more and more efficacy with simultaneous cost reduction. Adaptation of layered transition metal dichalcogenide as the host may be a potential answer to such challenges. The current study presents a theoretical in-depth analysis regarding improvement in efficient detection of NH3 using layered vanadium di-selenide (VSe2) with the introduction of point defects. The poor affinity between VSe2 and NH3 forbids the use of the former in the nano-sensing device's fabrications. The adsorption and electronic properties of VSe2 nanomaterials can be tuned with defect induction, which would modulate the sensing properties. The introduction of Se vacancy to pristine VSe2 was found to cause about an eight-fold increase (from -012 eV to -0.97 eV) in adsorption energy. A charge transfer from the N 2p orbital of NH3 to the V 3d orbital of VSe2 has been observed to cause appreciable NH3 detection by VSe2. In addition to that, the stability of the best-defected system has been confirmed through molecular dynamics simulation, and the possibility of repeated usability has been analyzed for calculating recovery time. Our theoretical results clearly indicate that Se-vacant layered VSe2 can be an efficient NH3 sensor if practically produced in the future. The presented results will thus potentially be useful for experimentalists in designing and developing VSe2-based NH3 sensors.

Enhancement of CO adsorption energy on defective graphene-supported Cu13 cluster and prediction with an induction energy model

The adsorption of CO on Cu13 and defective graphene-supported Cu13 clusters is investigated using ab initio molecular dynamics methods. The results show that the CO adsorption energies on the defective graphene-supported Cu13 cluster are substantially enhanced compared to those on the Cu13 cluster. Furthermore, the average adsorption energy on the defective graphene-supported Cu13 cluster is significantly increased by 155% compared with the experimental one on pristine Cu surfaces, indicating that the defective graphene-supported Cu13 cluster can be an excellent catalyst for CO adsorption. The enhancement of the adsorption energies can be qualitatively explained in terms of the crystal orbital Hamilton population, that is, as the bond interaction increases, the adsorption energy increases. We propose an induction energy model to calculate the amount of the adsorption energy enhancement. The predicted adsorption energies on the defective graphene-supported Cu13 clusters are in quantitative agreement with those obtained from ab initio molecular dynamics simulations. The current study provides insights into designing highly active catalysts for CO adsorption.

Why can cobalt(III) corrole form more stable metal/ organic interfaces than cobalt(II) porphyrin?

The ring size of tetrapyrrole ligands can dramatically influence the interfacial interactions of their metal complexes, as was found in a comparison of alkyl-substituted cobalt(II) porphyrins and cobalt(III) corroles adsorbed on a Ag(111) surface. The electronic properties of interfaces of both metal complexes were studied using photoelectron spectroscopy (XPS, UPS) and scanning tunneling microscopy (STM) in the monolayer and multilayer regimes. In the respective multilayers, the surface-decoupled complexes comprise paramagnetic cobalt centers, as indicated by the Co 2p core-level spectra. In the monolayers, both complexes are chemisorbed and engage in charge transfer at the interface. Consequently, the former singly occupied orbitals at the cobalt centers accept electron density from the Ag(111) surface. As a result, the cobalt centers of both complexes are reduced. Despite these similarities, there are substantial differences in the overall interaction strength: a much stronger interaction was observed in the case of the corrole complex, for which the interfacial charge transfer is not limited to the cobalt states, but also involves the ligand’s [Formula: see text]-electron system. Density functional theory (DFT) calculations of the corresponding parent macrocycles reveal that, in comparison with the porphyrin, the corrole exhibits increased adsorption energy, a reduced adsorption height, and undergoes a stronger interfacial charge transfer. The increased stability of the corrole/ metal interface is attributed to the corrole ligand’s open-shell character with delocalized [Formula: see text]-electron spin density and the resulting stabilization by rearomatization-driven electron transfer.

Surface modification of graphene with functionalized carbenes and their applications in the sensing of toxic gases: a DFT study.

Graphene and other 2D materials have gained significant attention in the development of gas sensors. In this study, we employed Density Functional Theory (DFT) to investigate the adsorption properties of diazomethanes (1a-1g) with various functional groups (R = OH (a), OMe (b), OEt (c), OPr (d), CF3 (e), Ph (f)) on pristine graphene. Furthermore, we explored the adsorption behavior of activated carbenes (2a-2g) generated from the decomposition of diazomethanes on graphene, as well as the functionalized graphene derivatives (3a-3g) resulting from [2 + 1] cycloaddition reactions between (2a-2g) and graphene. The interaction between these functionalized derivatives (3a-3g) and toxic gases was also investigated. Our results revealed that carbenes exhibited a stronger affinity for graphene compared to diazomethanes. The adsorption energy of esters (3b, 3c, and 3d) on graphene decreased relative to compound 3a, while 3e exhibited increased adsorption energy due to the electron-withdrawing effect of fluorine atoms. Additionally, the adsorption energy of phenyl and nitrophenyl groups (3f and 3g) decreased due to their π-stacking interaction with graphene. Importantly, all functionalized derivatives (3a-3g) demonstrated favorable interactions with gases. Notably, the derivative 3a, acting as a hydrogen bonding donor, exhibited superior performance. Furthermore, modified graphene derivatives exhibited the highest adsorption energy with NO2 gas, highlighting their potential for selective NO2 sensing applications. These findings contribute to the understanding of gas-sensing mechanisms and the design of novel graphene-based sensor platforms.

Computational designing of Au-decorated buckled bismuthene and its application as a humidity gas sensor

This research sought to determine the impact of humidity and the adsorption characteristics of CO, SO, SO2, NH3, and H2S on the surface of buckling bismuthene (b-Bi) adorned with Au for use in gas sensing applications. The density functional theory (DFT) including van der Waals dispersion utilized to investigate the gas sensing properties of environmentally friendly gases. All the gases exhibited physisorption except CO, which exhibited chemisorption. The Au-decorated b-Bi was found energetically stable and favorable due to its negative adsorption energy value. Moreover, the decoration of Au induces new states in the DOS and changes the nature of pure bismuthene to metallic. By adding Au to b-Bi, the CO gas's physisorption behavior transforms into chemisorption. According to the transmission results for CO and H2S gas molecules, these gases affect the system more significantly than SO, SO2, and NH3. Different famous properties were investigated in detail. Since the influence of humidity increases with an increase in adsorption energy, this type of material may continue to function even in the presence of humidity. This shows that the Au-decoration enhances the b-Bi potential for gas sensor applications.