scholarly journals Molecular Modeling of Ammonia Gas Adsorption onto the Kaolinite Surface with DFT Study

Minerals ◽  
2020 ◽  
Vol 10 (1) ◽  
pp. 46 ◽  
Author(s):  
Qi Cheng ◽  
Yongbing Li ◽  
Xiaojuan Qiao ◽  
Yang Guo ◽  
Yang Zhao ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Density Functional ◽  
Gas Adsorption ◽  
Hydroxyl Group ◽  
Partial Density ◽  
Hydroxyl Groups ◽  
High Porosity ◽  
Ammonia Gas ◽  
Nh3 Adsorption ◽  
Kaolinite Surface

With high porosity and being one of the most abundant clay minerals, dried kaolinite may be an excellent adsorbent to remove ammonia gas (NH3). Here, the plane wave pseudopotential method based on density functional theory (DFT) was used to explore the mechanism of ammonia gas adsorption on the dried kaolinite, the Mulliken electric charge, and the partial density of states of atoms of the NH3/kaolinite (001) system. NH3 adsorption on kaolinite can happen in three different type adsorption positions: “top”, “bridge” and “hollow”. The “hollow” position is enclosed by two "upright" hydroxyl groups perpendicular to the (001) surface of kaolinite and a "lying" hydroxyl group parallel to the surface. At this position, the adsorption is the most stable and has the highest adsorption energy. The nitrogen atom of the NH3 molecule bonds with the hydrogen atom in the "upright" hydroxyl group on the (001) surface and its hydrogen atom forms HN…O hydrogen bond with oxygen atom in the "lying" hydroxyl group, which leads to the NH3 stably adsorbed on kaolinite (001) surface. A small part of electrons transfer between NH3 molecules and kaolinite creates weakly electrostatic adsorption between them.

Activation of the Hydrogen-Terminated Diamond [100] by Hydrogen Atoms and Hydroxyl Groups

2020 ◽  
Vol 996 ◽  
pp. 151-156
Author(s):  
Xiao Gang Jian ◽  
Ji Bo Hu ◽  
Xin Huang ◽  
Pei Kang Yang ◽  
Jun Peng Wang
Keyword(s):  
Hydrogen Atom ◽  
Low Temperature ◽  
Density Functional ◽  
Diamond Surface ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Hydrogen Atoms ◽  
Activation Rate ◽  
Limiting Stage ◽  
Rate Limiting

The process of producing active vacancies on a hydrogen-terminated diamond surface is the most important rate-limiting stage in CH4/H2 and CH4/H2/CO2 atmospheres. Hydrogen atom and the hydroxyl group can bone to the hydrogen atom on the diamond surface and create an active vacancy. Density functional theory (DFT) was used to study the extraction reaction by two reactants both hydrogen atom and the hydroxyl group. The result indicated that the hydroxyl group could reduce the energy required for diamond surface activation. What is more, the activation rate of the surface by the hydroxyl group was livelier at low temperature, while the activation rate of the hydrogen atom predicts on the contrary. The scanning electron microscope (SEM) and Raman spectra demonstrated that the introduction of CO2 in the CH4/H2 atmosphere could reduce the deposition temperature and raise the deposition rate at low temperature.

scholarly journals Hydrolysis Mechanism of Bismuth in Chlorine Salt System Calculated by Density Functional Method

2020 ◽  
Vol 71 (6) ◽  
pp. 178-193
Author(s):  
Liao Chunfa ◽  
Xu Zhenxin ◽  
Zou Jianbai ◽  
Jiang Pinguoo
Keyword(s):  
Density Of States ◽  
Density Functional ◽  
Energy Gap ◽  
Density Functional Method ◽  
Covalent Bond ◽  
Salt System ◽  
Hydroxyl Group ◽  
Partial Density ◽  
Hydroxyl Groups ◽  
Total Density

Based on the density functional theory, this paper presents the calculated cellular electronic properties of BiCl3, BiOCl and Bi3O4Cl, including unit cell energy, band structure, total density of states, partial density of states, Mulliken population, overlapping population, etc. Combined with the thermodynamic analysis of Bi3+ hydrolysis process in chlorine salt system, the conversion mechanism of oxychloride bond in BiCl3 to form BiOCl and Bi3O4Cl by hydrolysis, ethanololysis and ethylene glycol alcohololysis was obtained by infrared spectroscopy. The results indicate that the energy of Bi3O4Cl cell system was lower than that of BiOCl cell, indicating that the structure of Bi3O4Cl was more stable. From the analysis of bond fluctuation, the electron nonlocality in BiOCl belt was relatively large, and the orbital expansibility was strong; thus the structure of BiOCl was relatively active. The state density map of Bi3O4Cl had the widest energy gap, i.e., the covalent bond between Bi3O4Cl was stronger than BiOCl. Therefore, the hydrolysis of BiCl3 would preferentially generate Bi3O4Cl with a more stable structure. The number of charge arrangement, overlapping population and infrared spectrogram indicate that there were two basic ways in the hydrolysis and alcoholysis of BiCl3. Firstly, two chlorine atoms in BiCl3 were replaced by hydroxyl groups ionized by water and alcohol to form [Bi(OH)2Cl] monomer, and BiOCl and Bi3O4Cl were formed by intra-molecular dehydration or inter-molecular dehydration. The other way was that the Bi atom directly reacted with the OH ionized by water and alcohol to form the [Bi-OH] monomer, and the Cl atom replaced the H atom on the hydroxyl group in the [Bi-OH] monomer to further form BiOCl and Bi3O4Cl.

scholarly journals Effects of Hydroxyl Group on the Interaction of Carboxylated Flavonoid Derivatives with S. Cerevisiae α-Glucosidase

2020 ◽  
Vol 16 (1) ◽  
pp. 31-44
Author(s):  
Huining Lu ◽  
Yanjiao Qi ◽  
Yaming Zhao ◽  
Nengzhi Jin
Keyword(s):  
Hydrogen Atom ◽  
Charge Density ◽  
Density Functional ◽  
Noncovalent Interactions ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Binding Affinities ◽  
Functional Theory ◽  
Density Analysis ◽  
Hydroxyl Hydrogen

Introduction: Carboxyalkyl flavonoids derivatives are considered as effective inhibitors in reducing post-prandial hyperglycaemia. Methods: Combined with Density Functional Theory (DFT) and the theory of Atoms in Molecules (AIM), molecular docking and charge density analysis are carried out to understand the molecular flexibility, charge density distribution and the electrostatic properties of these carboxyalkyl derivatives. Results: Results show that the electron density of the chemical bond C14-O17 on B ring of molecule II increases while O17-H18 decreases at the active site, suggesting the existence of weak noncovalent interactions, most prominent of which are H-bonding and electrostatic interaction. When hydroxyl groups are introduced, the highest positive electrostatic potentials are distributed near the B ring hydroxyl hydrogen atom and the carboxyl hydrogen atom on the A ring. It was reported that quercetin has a considerably inhibitory activity to S. cerevisiae α-glucosidase, from the binding affinities, it is suggested that the position and number of hydroxyl groups on the B and C rings are also pivotal to the hypoglycemic activity when the long carboxyalkyl group is introduced into the A ring. Conclusion: It is concluded that the presence of three well-defined zones in the structure, both hydrophobicity alkyl, hydrophilicity carboxyl and hydroxyl groups are necessary.

scholarly journals Theoretical Studies on the Mechanism of deNOx Process in Cu–Zn Bimetallic System—Comparison of FAU and MFI Zeolites

Molecules ◽  
2022 ◽  
Vol 27 (1) ◽  
pp. 300
Author(s):  
Izabela Kurzydym ◽  
Izabela Czekaj
Keyword(s):  
Density Functional ◽  
Co Adsorption ◽  
Computer Calculation ◽  
Zeolite Catalysts ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Hydrothermal Conditions ◽  
Fau Zeolite ◽  
Cu Catalyst ◽  
Mfi Zeolites

In the present study we propose a more promising catalyst for the deNOx process to eliminate harmful nitrogen oxides from the environment. The study was performed with a computer calculation using density functional theory (DFT) based on an ab initio method. Two zeolite catalysts, FAU and MFI, were selected with additional Cu–O–Zn bimetallic dimer adsorbed inside the pores of both zeolites. Based on the analysis of preliminary studies, the most probable way of co-adsorption of nitric oxide and ammonia was selected, which became the initial configuration for the reaction mechanism. Two types of mechanisms were proposed: with hydroxyl groups on a bridged position of the dimer or a hydroxyl group on one of the metal atoms of the dimer. Based on the results, it was determined that the FAU zeolite with a bimetallic dimer and an OH group on the zinc atom was the most efficient configuration with a relatively low energy barrier. The real advantage of the Cu–Zn system over FAU and MFI in hydrothermal conditions has been demonstrated in comparison to a conventional Cu–Cu catalyst.

Chemical Stability of 2D-Nanostructured WO3 in Hydrogen Sensing Under Varied Operation Temperature

NANO ◽  
2016 ◽  
Vol 11 (08) ◽  
pp. 1650092 ◽  
Author(s):  
Taisheng Yang ◽  
Hui Tian ◽  
Yue Zhang ◽  
Chen Li
Keyword(s):  
Water Molecule ◽  
Chemical Stability ◽  
Density Functional ◽  
Stable State ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Surface Hydroxyl ◽  
Hydrogen Sensing ◽  
Operation Temperature ◽  
Surface Hydroxyl Groups

Nanostructured metal oxide-based resistive-type gas sensors are of high research interest. Chemical stability is the most critical issue due to the surface electron species and density. In the present paper, 2D-nanostructured WO3 was prepared and characterized, and a WO3-based sensor was fabricated and analyzed. The results showed that the synthesized WO3 material exhibited nanosheet structure, and during hydrogen sensing testing, the current baseline shifted with various tendencies, even completely opposite directions under different operation temperatures. The chemistry analysis results indicated that water molecule and hydroxyl group were formed under low operation temperature but further oxidation occurred at higher temperatures. The adsorption of H2 on oxygen terminated WO3(0 0 1) surfaces by density functional theory (DFT) method indicated that a water molecule formed by adsorption of a hydrogen molecule at the O site with the most thermodynamically stable state, and two surface hydroxyl groups formed by dissociative adsorption with a thermodynamically less stable state. The water molecule and surface hydroxyl groups increased the conductivity of the WO3 film while that was decreased as the oxidation occurred.

scholarly journals Research on the Hydrophilicity of Non-Coal Kaolinite and Coal Kaolinite from the Viewpoint of Experiments and DFT Simulations

Symmetry ◽  
2020 ◽  
Vol 12 (7) ◽  
pp. 1199
Author(s):  
Peng Xi ◽  
Ruixin Ma ◽  
Wenli Liu
Keyword(s):  
Contact Angle ◽  
Hydrogen Atom ◽  
Oxygen Atom ◽  
Water Molecule ◽  
Density Functional ◽  
Physical Adsorption ◽  
Key Factor ◽  
The Difference ◽  
Kaolinite Surface ◽  
Single Water Molecule

Coal is often coated by coal kaolinite in flotation, resulting in an increase in concentrate ash. The natural hydrophilicity of minerals is the key factor to determining its flotation behavior. The results of studies on the contact angle of non-coal kaolinite and coal kaolinite samples found that the contact angle of coal kaolinite was bigger than that of non-coal kaolinite and the hydrophilicity of the latter was stronger. To investigate the mechanism of the hydrophilic difference between non-coal kaolinite and coal kaolinite, the adsorption of a single water molecule on non-coal kaolinite and coal kaolinite (100) and (00 1 ¯ ) surfaces was calculated with the first principle method of the density functional theory (DFT). The calculation results showed that hydrogen bonds were formed between the hydrogen atom and the oxygen atom of the surface and the hydrogen atom and the oxygen atom of the water molecule after the water molecule was adsorbed on the kaolinite (100) and (00 1 ¯ ) surface. The adsorption process of water molecules on the kaolinite surface was physical adsorption with Van der Waals force existing between them. Regardless of whether the kaolinite (001) surface or the kaolinite (00 1 ¯ ) surface was doped with a carbon atom, the adsorption of a single water molecule was weakened, with a weaker hydrogen bond formed. The calculated results explained the difference of hydrophilicity between non-coal kaolinite and coal kaolinite samples from the molecular and atomic viewpoint.

Chemical Analysis of Ultra-Thin DLC Films and Lubricant/DLC Interface Using Plasmonic Sensors

2014 ◽  
Author(s):  
M. Yanagisawa ◽  
M. Kunimoto ◽  
T. Homma
Keyword(s):  
Chemical Analysis ◽  
Raman Spectra ◽  
Density Functional ◽  
Chemical Interaction ◽  
Phenyl Group ◽  
Hydroxyl Group ◽  
Intensity Change ◽  
Hydroxyl Groups ◽  
Plasmonic Sensor ◽  
Nitrogenated Carbon

The technical potential of a new plasmonic sensor, which can acquire surface-enhanced Raman spectra with high sensitivity by controlling surface plasmons is demonstrated for the chemical analysis of diamond-like carbon (DLC) films, lubricant films, and the DLC/lubricant interface on magnetic disks of sub-nanometer scale. The Raman spectra of thin DLC films and lubricated DLC carbon can be acquired with a high S/N ratio. Raman spectra of lubricated DLC carbon can also be acquired with the high S/N ratio. The wavenumber shift and intensity change of the Raman peaks of the phenyl and hydroxyl groups in the mixed lubricants (ADOH and Z-tetraol) show that the chemical interaction with the DLC surfaces of the phenyl group in the lubricant molecule decreases with increasing nitrogen content, whereas that of the hydroxyl group with the nitrogenated carbon increases. Raman spectra of nitrogenated DLC films are also acquired, the peaks show good agreement with density functional theory calculations. The calculated bonding energy indicates that the hydroxyl groups interact with the nitrogenated carbon.

scholarly journals The study of the reactivity of derivatives of hydroxycinnamic alcohol as model compounds of lignin

2020 ◽  
Vol 61 (1) ◽  
pp. 33-39
Author(s):  
Oleg K. Karimov ◽  
◽  
Galina Yu. Kolchina ◽  
Eldar M. Movsumzade ◽  
◽  
...  
Keyword(s):  
Aromatic Ring ◽  
Density Functional ◽  
Nucleophilic Attack ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Model Compounds ◽  
Hartree Fock ◽  
A Charge ◽  
Derivatives Of ◽  
Hybrid Density Functional

In the framework of method of the B3LYP hybrid density functional and the restricted Hartree-Fock method in the basis of 6-311 (d, p), quantum-chemical calculations of model compounds of lignin, i.e. derivatives of p-hydroxycinnamic alcohol were carried out. The structures and reactivity of coumaric, coniferyl and synapol alcohols were studied. The structural units of lignin contain hydroxyl groups which can be in the plane of benzene ring but can be turned up to 90° with respect to this plane. In the case of methoxy groups which are also present in coniferol and synapol alcohols, the methyl group is turned to 90° with respect to the plane of ring, as the most favorable conformation. Moreover, these compounds contain π,π-conjugations of the aromatic ring with an aliphatic fragment of molecule that affects the geometric characteristics of the molecule. For coumaric and coniferyl alcohols, the Сар–Сα bond length is 1.47 Ǻ. A slight deformation of valence angles for coumaric and synapol alcohols equal to 118.94° and 117.72° respectively instead of 120° at sp2 hybridization indicates the availability of conjugation. The use of a charge as a descriptor of attack selectivity of nucleophilic and electrophilic particles allows us to analized of the reactivity of these acids are given. It is found that the electronic structure of lignin is determined primarily by the charge distribution in its structural phenylpropane unit. In the molecules of all model compounds of lignin, the center for nucleophilic attack is the carbon of aromatic ring (E-ring) with a hydroxyl group, and in the molecule of synapol alcohol, this center is also the carbon of the aromatic ring (E-ring) with a methoxy group. In all three compounds, a center with an increased electron density appears on the Сβ carbon atom.

Influence of intramolecular interactions on carbon dioxide gas adsorption capacity in Mesoporous Imine polymers

2018 ◽  
Author(s):  
Jaya Prakash Madda ◽  
Pilli Govindaiah ◽  
Sushant Kumar Jena ◽  
Sabbhavat Krishna ◽  
Rupak Kishor
Keyword(s):  
Carbon Dioxide ◽  
Adsorption Capacity ◽  
Density Functional ◽  
Gas Adsorption ◽  
Ambient Pressure ◽  
Condensation Reaction ◽  
Intramolecular Interactions ◽  
Carbon Dioxide Adsorption ◽  
Nitrogen Gas ◽  
Adsorption Characteristic

<p>Covalent organic Imine polymers with intrinsic meso-porosity were synthesized by condensation reaction between 4,4-diamino diphenyl methane and (para/meta/ortho)-phthaladehyde. Even though these polymers were synthesized from precursors of bis-bis covalent link mode, the bulk materials were micrometer size particles with intrinsic mesoporous enables nitrogen as well as carbon dioxide adsorption in the void spaces. These polymers were showed stability up to 260<sup>o</sup> centigrade. Nitrogen gas adsorption capacity up to 250 cc/g in the ambient pressure was observed with type III adsorption characteristic nature. Carbon dioxide adsorption experiments reveal the possible terminal amine functional group to carbamate with CO<sub>2</sub> gas molecule to the polymers. One of the imine polymers, COP-3 showed more carbon dioxide sorption capacity and isosteric heat of adsorption (Q<sub>st</sub>) than COP-1 and COP-2 at 273 K even though COP-3 had lower porosity for nitrogen gas than COP-1 and COP-2. We explained the trends in gas adsorption capacities and Qst values as a consequence of the intra molecular interactions confirmed by Density Functional Theory computational experiments on small molecular fragments.</p>

scholarly journals Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2131
Author(s):  
Leonardo Dalseno Antonino ◽  
Júlia Rocha Gouveia ◽  
Rogério Ramos de Sousa Júnior ◽  
Guilherme Elias Saltarelli Garcia ◽  
Luara Carneiro Gobbo ◽  
...  
Keyword(s):  
Experimental Work ◽  
Chemical Structure ◽  
31P Nmr ◽  
Kraft Lignin ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Diphenylmethane Diisocyanate ◽  
Complex Chemical ◽  
Heterogeneous Reactivity ◽  
Phenolic Hydroxyl Groups

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. 31P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.

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