Calculated Adsorption Energies Research Articles

Physical Adsorption and Raman Spectra of Hydrazine Hydrate on the Graphene Surface.

In experimental studies, hydrazine hydrate is widely employed as a reducing agent for the conversion of graphene oxide to graphene. Herein, we conducted theoretical calculations using cluster models to investigate the adsorption behavior of hydrazine hydrate on the surface of graphene. The calculated adsorption energy reveals that hydrazine hydrate can physically bind to the graphene surface. Our findings indicate that two hydrogen bonds stabilize the hydrazine hydrate molecule, while its adsorption onto the graphene surface is primarily driven by van der Waals forces. By combining computational simulations and experimental measurements, we thoroughly examined the Raman spectra of both free and adsorbed hydrazine hydrates, which enabled us to gain detailed insights into their molecular vibrations. Notably, in the Raman spectra of free hydrazine hydrate, a strong peak at around 3300 cm-1 corresponds to the NH2 vibration. Similarly, peaks near 3300 cm-1 were observed in the Raman spectra of graphene with adsorbed hydrazine hydrate molecules. The results are expected to provide valuable references for future experimental investigations involving hydrazine hydrate.

Synthesis and characterization of magnetic aluminum metal-organic frameworks encapsulated with chitosan and carboxymethyl cellulose for effective elimination of atrazine from aqueous solutions: Adsorption evaluation, DFT calculations and Box-Behnken design optimization

The discharge of herbicides is a primary contributor to water contamination, presenting significant environmental and public health hazards. Encapsulating herbicides in a chemical compound called MAl-MOF/CS-CMC hydrogel bead (MACC) made from magnetic aluminum metal-organic frameworks (MAl-MOF) and crosslinked with chitosan (CS) and carboxymethyl cellulose (CMC) shows promise for potential use. The research successfully developed and examined MACC microspheres, utilizing various analytical techniques including PXRD, FESEM, TEM, FT-IR, and XPS. The efficiency of MACC in eliminating atrazine (ATZ) from wastewater was also simulated. Additionally, density functional theory (DFT) was employed to assess the electrical characteristics, reactivity, and arrangement of ATZ at a structural level. The results of the DFT analysis demonstrate a significant relationship between the locations of nucleophilic and electrophilic attacks and the molecular orbitals of the HOMO and LUMO. Using MACC as an adsorbent provides considerable advantages due to its expansive surface area of 860.92 m2/g and a pore size of 1.48 nm, meeting the mesoporous classification criteria outlined by IUPAC standards. In addition, it possesses a pore volume of 1.22 cm3/g. Nevertheless, following the adsorption procedure, the pore volume reduced to 0.78 cm3/g, and the surface area decreased to 650.42 m2/g. Several factors contributing to the capacity to attract and retain substances were analyzed. These factors encompass temperature, duration of contact, quantity of the attracting substance, initial atrazine (ATZ) concentration, and solution pH. The primary method of adsorption that was determined is chemisorption, as evidenced by the calculated adsorption energy of 29.3 kJ per mole. The thermodynamic analysis indicates that the adsorption of ATZ by the micropores of MACC occurs spontaneously and is characterized as endothermic, as evidenced by the positive ΔHo value and negative ΔGo value. It has been proposed that a range of adsorption mechanisms, including chemisorption, π-π interactions, pore filling, hydrogen bonding, and electrostatic interactions, may be responsible for removing the herbicide from the MACC material.

Molybdenum Induced Modifications in the Quantum Capacitance of Graphene‐Based Supercapacitor Electrodes: First‐Principle Calculations

Herein, spin‐polarized calculation is performed based on density‐functional theory in the frame of generalized gradient approximation to examine the quantum capacitance (CQ) and surface charge storage of graphene(G)‐based supercapacitor electrodes modified with molybdenum, sulfur, nitrogen, and monovacancy. In total, 15 electrode models, including graphitic doping, monovacancy doping, and Mo adsorption on pristine and single‐vacancy graphene structures are analyzed. In the results, it is demonstrated that vacancy defects and N/S/Mo doping enhances the CQ of graphene. Among all configurations, pyrrolic‐S (d1S) shows the lowest CQ performance due to few states at the Fermi level. Electrodes with Mo adsorption exhibit the highest CQ, particularly when Mo is adsorbed at the top site of graphene. However, formation and adsorption energy calculations suggest that Mo is more likely to adsorb at hollow sites. Optimally, Mo can be most effectively utilized by loading it onto vacancy or N/S‐decorated vacancy sites. The significant contribution of Mo's 4dz2 and 4s states to CQ, along with the charge‐redistribution around the Mo complexes, may facilitate proton‐coupled electron transfer to enhance pseudocapacitance. In these findings, valuable insights into designing high quantum capacitance of 2D materials with electroactive sites for improved energy storage are offered.

Adsorption of molecular hydrogen (H2) on a fullerene (C60) surface: insights from density functional theory and molecular dynamics simulation.

Understanding the adsorption behavior of molecular hydrogen (H2) on solid surfaces is essential for a variety of technological applications, including hydrogen storage and catalysis. We examined the adsorption of H2 (∼2800 configurations) molecules on the surface of fullerene (C60) using a combined approach of density functional theory (DFT) and molecular dynamics (MD) simulations with an improved Lennard-Jones (ILJ) potential force field. First, we determined the adsorption energies and geometries of H2 on the C60 surface using DFT calculations. Calculations of the electronic structure help elucidate underlying mechanisms administrating the adsorption process by revealing how H2 molecules interact with the C60 surface. In addition, molecular dynamics simulations were performed to examine the dynamic behavior of H2 molecules on the C60 surface. We accurately depicted the intermolecular interactions between H2 and C60, as well as the collective behavior of adsorbed H2 molecules, using an ILJ potential force field. Our findings indicate that H2 molecules exhibit robust physisorption on the C60 surface, forming stable adsorption structures with favorable adsorption energies. Calculated adsorption energies and binding sites are useful for designing efficient hydrogen storage materials and comprehending the nature of hydrogen's interactions with carbon-based nanostructures. This research provides a comprehensive understanding of H2 adsorption on the C60 surface by combining the theoretical framework of DFT calculations with the dynamical perspective of MD simulations. The outcomes of the present research provide new insights into the fields of hydrogen storage and carbon-based nanomaterials, facilitating the development of efficient hydrogen storage systems and advancing the use of molecular hydrogen in a variety of applications.

Interfacial adsorption of ionic liquids (ILs) on graphitic carbon nitride (g-C3N4) nanosheets: A DFT study

The adsorption of nine common ionic liquids (ILs) on two well-known structures of graphitic carbon nitride (g-C3N4) nanosheets, including Triazine-g-C3N4 and Heptazine-g-C3N4 has been investigated using density functional theory (DFT) method in gas phase and water solvent. The interactions between the ILs and the nanosheets are characterized by several techniques, such as quantum theory of atoms in molecules (QTAIM) analysis, noncovalent interaction (NCI) plots, and energy decomposition analysis (EDA) method. Interestingly, the obtained results showed that electrostatic interactions have the highest contributions to the interaction energies between the ILs and the surfaces, followed by dispersion interactions and orbital interactions (ΔEelec > ΔEdisp > ΔEorb) The most important Van der Waals (vdW) interactions between the ILs and the surfaces include π–π, CH…N, CH…π (CN), and CN…X (X = F, N, O) interactions. On the other hand, the adsorption of ILs is accompanied by charge transfer from the surfaces to the ILs. The calculated adsorption energy (Eads) showed that the [Bmim][PF6] IL has the highest adsorption affinity on the Triazine-g-C3N4 (−28.28 kcal/mol) and Heptazine-g-C3N4 (−26.68 kcal/mol) surfaces. Thermochemistry calculations showed that the Eads, ΔHads, and ΔGads values of IL@surface complexes decrease on moving from gas phase to water media. However, our results showed that the adsorption of ILs on the surfaces is still exothermic and proceeds spontaneously. Upon adsorption of ILs, a decrease in the HOMO–LUMO energy gap (Eg) is observed and is accompanied by an increase in the reactivity and electrophilic character of the surfaces. TD-DFT calculations showed that the weak adsorption of ILs leads to small red or blue shifts in the absorption bands of the Triazine-g-C3N4 and Heptazine-g-C3N4 surfaces. However, no significant changes are observed in the shape of the absorption spectra of the surfaces. Furthermore, the transition density matrix (TDM) heat maps of the IL@surface complexes showed that the electrons and holes are generally concentrated on the Triazine-g-C3N4 and Heptazine-g-C3N4 surfaces in the IL@surface complexes, signifying that the electronic transitions occur mainly on the surfaces.

Investigation of the adsorption behaviors of novel Au3 cluster decorated arsenene nanosheets towards thiophene and methanethiol detection: A DFT study

First principles calculations were carried out to describe the interactions between Aun-arsenene nanosheets and methanethiol/thiophene molecules. Both Au-arsenene and Au3-arsenene nanosheets exhibit smaller band gap than the pure arsenene system due to the emergence of new energy bands near the Fermi level. Thus, the conductivity and sensor capabilities are significantly enhanced for the Au functionalized arsenene nanosheets. Calculated formation energies of −2.38 eV and −5.37 eV for Au-arsenene and Au3-arsenene nanosheets indicate their structural stability. The adsorption of methanethiol and thiophene molecules on the Au-arsenene substrates spontaneously occurs due to the negative calculated adsorption energies. Besides, thiophene molecule exhibits the highest adsorption energy (−0.52 eV) on the Au-arsenene substrate through its S atom strongly connected to the Au atom. The moderate adsorption energies indicate the shorter recovery times for sensing applications. Our work sheds light on the exploration of Au-arsenene as an effective candidate for sensing methanethiol and thiophene molecules.

Study on the influence of corrosion degree on the high-temperature oxidation and combustion characteristics of AZ91, WE43 and ZE10 magnesium alloys

Based on magnesium alloy materials, different degrees of corrosion occur on the surface during use, and the corrosion state significantly affects its high-temperature oxidation and combustion characteristics. This study examines various corrosion conditions, investigates the impact of different corrosion levels on the combustion characteristics of magnesium alloys, and analyses the adsorption performance, state density, and oxygen atom diffusion barrier of alloy elements in AZ91, WE43, and ZE10 magnesium alloys based on first-principles calculations. It reveals the mechanism of the impact of each alloy element on the surface oxide film of magnesium alloys and explains the principles of the experimental results. The results indicate that with increasing corrosion time, temperature, and pressure, the time for the surface oxide film to rupture significantly decreases. In the six magnesium alloy systems of quantum calculations, the Mg–Re structure exhibits the strongest stability. According to adsorption energy calculations, the Mg–Al and Mg–Y systems show the best oxygen adsorption performance. Magnesium alloys doped with Y and Ce elements have the highest oxygen atom diffusion barrier. Hence, magnesium alloy systems doped with Y and Ce elements have a dense surface oxide film that remains undamaged even at very high temperatures, demonstrating excellent high-temperature corrosion resistance and providing an explanation for the experimental results.

Curvature-Induced Electron Spin Catalysis with Carbon Spheres.

Here, we report curvature-induced electron spin catalysis by using solid carbon spheres as catalysts, which were synthesized using positive curvature molecular hexabromocyclopentadiene as a precursor molecule, following a radical coupling mechanism. The curvature spin of carbon is regarded as an overlapping state of σ- and π-radical, which is identified by the inverse Laplace transform of pulse-electron paramagnetic resonance. The growth mechanism of carbon spheres abiding by Kroto's model, is supported by the density functional theory study of thermodynamics and kinetics calculations. The solid carbon spheres present excellent catalytic behaviour of oxidation coupling of amines to form corresponding imines with the conversion of >99 %, selectivity of 98.7 %, and yield of 97.7 %, which is attributed to the predominantly curvature-induced electron spin catalysis of carbon, supported by the calculation of oxygen adsorption energy. This work proposes a view of curvature-induced spin catalysis of carbon, which opens up a research direction for curvature-induced electron spin catalysis.

Curvature‐Induced Electron Spin Catalysis with Carbon Spheres

AbstractHere, we report curvature‐induced electron spin catalysis by using solid carbon spheres as catalysts, which were synthesized using positive curvature molecular hexabromocyclopentadiene as a precursor molecule, following a radical coupling mechanism. The curvature spin of carbon is regarded as an overlapping state of σ‐ and π‐radical, which is identified by the inverse Laplace transform of pulse‐electron paramagnetic resonance. The growth mechanism of carbon spheres abiding by Kroto's model, is supported by the density functional theory study of thermodynamics and kinetics calculations. The solid carbon spheres present excellent catalytic behaviour of oxidation coupling of amines to form corresponding imines with the conversion of >99 %, selectivity of 98.7 %, and yield of 97.7 %, which is attributed to the predominantly curvature‐induced electron spin catalysis of carbon, supported by the calculation of oxygen adsorption energy. This work proposes a view of curvature‐induced spin catalysis of carbon, which opens up a research direction for curvature‐induced electron spin catalysis.

Designing Mo-based transition metal dichalcogenides for sustainable hydrogen production: Anionic substitution and DFT insight

Anionic substitution is an effective approach to optimize the catalytic activity of Mo based transition metal dichalcogenide (TMD)- MoS2 towards hydrogen evolution reaction (HER). By optimizing the S-to-Se ratio, materials with the ideal Gibbs free energy of hydrogen adsorption (ΔGH) values are synthesized (MoS2, MoS1.4Se0.6, MoS1.2Se0.8, MoSSe, MoSe2) and their HER performance is examined in 0.5 M H2SO4 solution. Density functional theory calculations of hydrogen adsorption energy on the surface of the electrocatalysts show that Se substitution facilitates electron transfer between the catalyst surface and the hydrogen donor, thereby lowering the additional potential required for water splitting, making MoS1.2Se0.8 the most favorable HER electrocatalyst with the lowest value of adsorption energy. Further enhancement in the electrocatalytic activity of mixed anion TMDs has been achieved by the incorporation of carbon nanotubes (CNTs). MoS1.2Se 0.8-CNT nanocomposite exhibits superior HER performance with an overpotential of 118 mV and a Tafel slope of 63 mV/decade as compared to MoS1.2Se0.8 sample owing to the synergetic effect from CNTs and MoS1.2Se0.8.

Structural and energetic properties of cluster models of anatase-supported single late transition metal atoms: a density functional theory benchmark study.

Single-atom catalytic systems constitute an intriguing research topic due to their inherently different chemical behavior as compared to classic heterogeneous catalysts. In this study, cluster systems representing single late transition metal atoms adsorbed on anatase were constructed starting from previously generated periodic models and subjected to a density functional theory (DFT) benchmark study. The ability of different density functional approximations representing all rungs of the Jacob's Ladder classification to accurately describe bond lengths and adsorption energies was assessed for these clusters with the aim of revealing the functional that allows to retain the structural characteristics of the initial periodic system, while also delivering reliable energetics. In this regard, our results indicate that optimisation of the clusters with the meta-GGA functionals TPSS or RevTPSS provides the lowest mean unsigned error and root-mean-square deviations with respect to the periodic models. Moreover, these functionals and, to a slightly lesser degree, PW91 were also found to provide adsorption energies that are statistically the least deviating from the CCSD(T) reference data. More complex hybrid functionals appear to be performing less well. Cluster geometries were determined at the Kohn-Sham DFT level using the LANL2DZ basis set for the transition metals and the Pople 6-31G(d) basis set for O and H. The density functional approximations considered were SVWN, PBE, BP86, BLYP, PW91, TPSS, RevTPSS, M06L, M11L, B3LYP, PBE0, M06, M06-2X, MN15, ωB97X-D, CAM-B3LYP, M11, and MN12-SX. Reference adsorption energies of the metals on the support cluster were obtained at the CCSD(T)/LANL2TZ (transition metals)/6-311 + + G(d,p)//RevTPSS/LANLD2DZ (transition metals)/6-31G*. Besides the above-mentioned functionals, energy calculations using the double-hybrid functionals, DSDPBEP86, PBE0-DH, and B2PLYP, were also performed. All adsorption energy calculations were carried out on the RevTPSS geometries.

Theoretical insights of 2D Fe3GeTe2/In2Se3 multiferroic vdW heterostructure based gas sensors for high-performance NO detecting

The impact of the harmful gas NO on the atmospheric environment cannot be ignored, so it is necessary to develop efficient gas sensors to detect and absorb NO at room temperature. In this work, we systematically explored the electron transport properties and gas sensing properties of Fe3GeTe2, In2Se3 monolayers and its multiferroic van der Waals (vdW) heterostructures of Fe3GeTe2/In2Se3 for detecting NO by using density functional theory and nonequilibrium Green's function methods. The calculated adsorption energies, electron localisation functions, band structures and density of states indicate that its a chemisorption for the adsorption of NO on Fe3GeTe2 and a physisorption on In2Se3, while the specific adsorption style is highly dependent on the stacking and molecular adsorption sites of different Fe3GeTe2/In2Se3 structures. In addition, the pristine Fe3GeTe2 monolayer and Fe3GeTe2/In2Se3 based nanodevices realized a significant anisotropy for electron transport along the zigzag and armchair directions, and their anisotropic maximum current ratios in the zigzag to armchair directions were 1.90 and 1.89. Meanwhile, the NO sensitivity ratio of Fe3GeTe2 and Fe3GeTe2/In2Se3 based gas sensors can be up to 79 % and 107 %, respectively. This highlights a notably superior gas-sensitive performance of the Fe3GeTe2/In2Se3 heterostructure compared to the Fe3GeTe2 monolayer gas devices. These findings provide valuable references for the application of multiferroic heterostructures in the field of gas sensors.

Density functional theory investigation of hypervalent iodine KICl2 passivation at PbI2 vacancy sites on the MAPbI3 surface

This study explores the impact of hypervalent KICl2 passivation on the electronic properties and stability of MAPbI3 perovskite slabs with PbI2 vacancies using density functional theory (DFT). Adsorption energy calculations reveal that KICl2 exhibits stronger binding energy (−4.73 eV) compared to O2 (−3.32 eV) and H2O (−3.28 eV), indicating higher stability on the MAPbI3 surface. However, due to the potential for KICl2 to dissociate into KCl and ICl in solution, these compounds were also evaluated as alternative passivation agents. The surface free energy of the KICl2-passivated slab is the lowest among the configurations studied, further confirming its enhanced surface stability. The projected density of states (PDOS) and band structure analyses show that KICl2 passivation introduces defect states near the conduction band minimum (CBM), reducing the bandgap from 1.89 eV (clean surface) to 1.81 eV. These defect states, contributed by Cl-3p and I-5p orbitals, enhance charge separation, potentially improving carrier collection. In contrast, the KCl-ICl passivated surface exhibits flat states near valence band edge, which could increase hole density and reduce hole mobility. Optical absorption calculations indicate that the KICl2-passivated surface shows stronger absorption in the 3–7 eV range. These findings suggest that KICl2 passivation improves both the electronic properties and surface stability of MAPbI3, offering a promising strategy for enhancing perovskite solar cell efficiency.

Unveiling the adsorption mechanism of propanehydrazine derivatives on magnesium oxide surface: Insights from computational approach

The use of green and effective inhibitors for preventing metal oxide (MgO) corrosion in industrial applications is highly significant in promoting environmental protection and sustainable development. This study delves into the adsorption behavior and interfacial mechanism of environmentally friendly inhibitor derived from propane hydrazine (PH) on MgO surface. Specifically, PH1, PH2, PH3, and PH4 were explored for their effectiveness in preventing corrosion by using advanced theoretical simulations-based density functional theory (DFT) for assessing the reactivity and adsorption characteristics. The study considered a detailed exploration of local and global reactivity descriptors, providing insights into the inhibitors’ reactivity and adsorption abilities in both isolated and adsorbed states. These findings focus more in the mechanisms underlying organic-inorganic interactions and present promising prospects for further development and application. Using first-principles DFT calculations alongside quantitative molecular surface analyses, we examined the adsorption patterns of PHs on the MgO(100) surface. These investigations are boosted by the application of independent gradient model (IGM) framework, providing robust verification of PHs' adsorption behavior on MgO(100) surface. Our calculations reveal a substantial decrease in the energy gap following complex formation, suggesting that charge density changes occur upon interaction with MgO surfaces, thereby facilitating direct electron transfer in all the studied systems. Noreover, the results highlight the crucial role of intermolecular interactions in boosting the interaction between PHs and the [Mg(H2O)6]2+ cation. First-principles DFT calculations show that all PH molecules consistently display parallel adsorption on the MgO surface, where the oxygen atoms form bonds with adjacent magnesium atoms. The bond lengths vary from 2.18 to 2.35 Å when PHs bind to the Mg atoms in parallel orientations through the oxygen atom, suggesting a stable parallel arrangement for PH molecules on the MgO surface. The calculated adsorption energy (Eads) varies in the following order: MgO-PH3 (−815.14 Kcal mol−1) > MgO-PH2 (−803.85 Kcal mol−1)) > MgO-PH4 (−695.38 Kcal mol−1) > MgO-PH1 (−125.77 Kcal mol−1). This trend indicates that parallel interactions enhance the adsorption behavior and binding of PH compounds through inter- and intra-molecular interactions, resulting in the PHs being centered at specific sites on the MgO surface. The potential enhancement in electrochemical properties is believed to stem from the synergistic interaction between the PHs and the MgO surface, which theoretically allows for a precise adjustment of their adsorption and interaction within the composite structure. This understanding provides a fundamental framework for examining the complex interfacial dynamics between inhibitor structures and elucidating how these molecular interactions influence the selection of corrosion inhibitors and their adsorption behaviors on the corrosion layer's surface, rather than on metallic Mg.

Group VIII Transition Metal (Fe, Ru & Os) Embedded Graphitic Carbon Nitride as an Acetone Sensor: A First Principle Investigation

This study investigates the acetone sensing behavior of pristine graphitic carbon nitride (gCN) and group VIII transition metal (Fe, Ru & Os) embedded gCN monolayer using DFT calculations. Key structural and electronic properties such as adsorption energy, band structure, and density of states (DOS) have been examined. The calculated adsorption energy of pristine gCN is −1.32 eV, which improves to –3.52, −2.75, and −1.73 eV for Fe, Ru, and Os embedded gCN, respectively. The band structure also indicates a reduction in the band gap of gCN after acetone adsorption due to the introduction of Fe, Ru, and Os. Furthermore, after the adsorption of acetone, the DOS values exhibit a significant increase from 13.48 eV−1 for pristine gCN to 439, 423, and 332 eV−1 for Fe, Ru, and Os embedded gCN, respectively.

Adsorption of phenolic compounds on polymeric ionic liquids: Adsorption isotherms interpretation and thermodynamic study

This study describes the thermodynamic assessment and steric interpretation of the 4-nitrophenol (4-NP) and 4-chlorophenol (4-CP) adsorption on polymeric ionic liquids (PILs) using advanced statistical physics model. A monolayer model with a single energy level was employed to elucidate the adsorption mechanisms of these phenolic compounds. The results showed that the orientation of 4-NP and 4-CP on the surface of this adsorbent was a combination of parallel and non-parallel configurations at the tested adsorption temperatures. The values of the adsorption capacities at saturation were 484.7 and 406.7 mg/g for4-NP and 4-CP, respectively. The modelling results indicated that more active sites from PILs surface were involved in the removal of 4-nitrophenol than those required for the 4-chlorophenol adsorption. The calculation of adsorption energies confirmed that the adsorption of 4-NP and 4-CP on PILs was exothermic and driven by physical forces involving hydrogen bonds and van der Waals forces. Three thermodynamic functions were analyzed to complete the macroscopic analysis of the adsorption mechanism for these relevant phenolic contaminants.

First-principles study of O3 molecule adsorption on pristine, N, Ga-doped and -Ga-N- co-doped graphene

The adsorption of O3 molecules (ozone) on graphene, N-doped graphene, Ga-doped graphene, and -Ga-N- co-doped graphene with an emphasis on O3 detection was examined in this work. The physical characteristics of -Ga-N-co-doped graphene are significantly altered upon O3 adsorption, which makes it a suitable choice for O3 detection molecular sensors. The interaction between the O3 molecule and the adsorbent is explained on the basis of their adsorption energy, adsorption distance and charge transfer. It was found that the adsorption of ozone molecules on the -Ga-N- co-doped graphene was more favorable in energy than that on the pristine one, representing the superior sensing performance of -Ga-N- co-doped system. In our work, we estimated the charge transfer between the O3 molecule and doped graphene nanostructures based on Mulliken population analysis. The calculated adsorption energy value shows the ozone molecule more firmly adsorbs on the surface of -Ga-N- co-doped graphene nanostructures (Eads = –1.74 eV) than that of pristine graphene (Eads = –0.41 eV), deriving from a stronger covalent bond between the ozone molecule and the -Ga- N- co-doped graphene nanostructures. Our findings thus suggest that -Ga-N- co-doped graphene could be a highly efficient gas sensor device for O3 detection in the environment.

Selective Separation of C8 Aromatics by an Interpenetrating Metal-Organic Framework Material.

O-xylene (OX) is an important chemical raw material, but it is often produced in mixtures with other C8 aromatics. Similar physicochemical properties of the C8 isomers make their separation and purification very difficult and energy intensive. There is an unmet need for an adsorbent that would be effective for the separation of OX from the other C8 isomers. This work reports a three-dimensional interpenetrated metal-organic framework, SYUCT-110, that interacts with each of the single-component C8 isomers to form. The selectivity of C8 aromatic hydrocarbons was determined through liquid-phase batch uptake experiments. The results revealed that the selectivity order was OX > PX > MX > ethylbenzene (EB). The selectivity values were found to be 2.63, 1.58, 5.51, 3.71, 1.86, and 3.02 for OX/MX, OX/PX, OX/EB, PX/MX, MX/EB, and PX/EB, respectively. The adsorption capacity of OX was 71 mg/g. Grand Canonical Monte Carlo simulations were used to study the C8 adsorption sites, revealing that π···π interactions are the main reason for the observed adsorption selectivity. The adsorption energy calculation results also verified the selectivity of SYUCT-110 for the synthesis of OX.

Insights into the Effect of a Microwave Field on the Properties of Modified γ-Alumina: A DFT Study

γ-Alumina is often used as a support for hydrodesulfurization catalysts due to its excellent performance. During the catalytic reaction, the strong surface acidity of γ-alumina can induce a strong interaction between the active phase and the support. The reaction activity of the catalyst can be affected by changing the present mode of the active phase on the surface of the support. The (110) crystal plane, acting as the strongest acidity plane of γ-alumina, was selected for modification. The supports modified with boron and phosphorus were successfully constructed, and the acid strengths were quantified by simulating the adsorption of the relevant probe molecules: pyridine in correlation with surface electronic properties via density functional theory. The surface adsorption energy calculation shows that the boron-modified surface is able to moderately reduce the adsorption capacity of alumina, while that of the surface modified by phosphorus is found to be enhanced over the sites of a tetrahedral coordination structure; however, at the other unsaturated Al sites, this is obviously reduced. The results of introducing electric fields imply that applying horizontal electric fields changes the surface acidity of alumina under the premise of a stable structure. With the enhancement of the horizontal electric fields, the adsorption capacity of tetra-coordination sites on the original surface gradually decreases, while those of the others gradually increases. However, for the boron-modified surface, introducing horizontal electric fields can reduce the adsorption capacity of all sites. Hence, microwave-electric-field-assisted modification of B further reduces the surface acidity of alumina, making it beneficial for deep hydrodesulfurization reactions.

A Study Based on the First-Principle Study of the Adsorption and Sensing Properties of Mo-Doped WSe2 for N2O, CO2, and CH4

As industry continues to develop rapidly, the greenhouse effect is becoming increasingly severe. CO2, CH4, and N2O are the three primary greenhouse gases, making their effective monitoring a crucial step in reducing emissions. This paper investigates the gas sensing performance of Mo-doped WSe2 for these three gases, through a theoretical study. First, using first-principles calculations, the doping behavior of Mo in WSe2 is examined. Subsequently, the adsorption properties of Mo-WSe2 for CO2, CH4, and N2O are analyzed by calculating adsorption energy, charge transfer, the electron localization function (ELF), Hirshfeld partition (IGMH), and the density of states (DOSs), culminating in an analysis of its sensing properties. The results indicate that when Mo is positioned above the upper Se atom, the structure is most stable. Therefore, this position is selected as the optimal adsorption site for studying the adsorption of the three gases. The adsorption energies for CO2, CH4, and N2O are 1.349 eV, −1.194 eV, and −0.528 eV, respectively, with corresponding charge transfers of 0.418, 0.450, and 0.115. In the N2O and CO2 adsorption systems, significant adsorption energy and charge transfer are observed, leading to relatively better adsorption compared to the CH4 system. Additionally, considering the adsorption performance, Mo-WSe2 demonstrates good sensor response and desorption times for N2O and CO2 at temperatures above 298 K. The findings of this research provide theoretical guidance for the application of Mo-WSe2 as a gas sensing material for detecting greenhouse gases.