CO and NO adsorption on copper-containing zeolite. A theoretical ab initio study

Ab initio calculations were performed to simulate the interaction between CO or NO and copper-containing zeolite at the SCF level. The zeolite catalysts were modelled by a molecular cluster of composition H₈Si₃AlO₄Cu⁺ with = 0, 1. For = 0 the oxidation state of the Cu atom corresponds to 1+ in Cu⁺/zeolite, while for° = 1 it is equal to 2+ in Cu²⁺/zeolite. It was found that only Cu⁺/zeolite should be responsible for CO and NO adsorption from the gas phase. The calculated heats of adsorption compare well with available experimental data and together with adsorption geometries allow us to interpret the observed IR data.     

Predicting the reactivity of phenolic compounds with formaldehyde under basic conditions: An ab initio study

A method is needed to predict which compounds, from the many alternative phenolic compounds, might be best for making polymeric phenolic systems. Kinetic data for the reaction of a series of phenolic compounds with formaldehyde using a base catalysis are available in the literature. Semiempirical calculations, using RHF/PM3, and ab initio calculations, using RHF/6‐31G, RHF/6‐31+G, and B3LYP/6‐311+G(2d,p), were performed on the series of phenolic compounds to determine their relative reactivities. Atomic charges were determined for the phenolate anions. For each compound, I summed the absolute value of the calculated, negative charges residing on carbon atoms of the phenolic ring at which the HOMO was located and at which no substituent was present to cause steric interference with the reaction. The sum of the charges for each compound was then regressed against the log of the relative reaction rate for that compound. The sum of charges from PM3‐based calculations gave poor correlation with reactivity. The sums of charges calculated by the CHelpG and Merz–Kollman/Singh methods at the ab initio levels of theory give excellent correlations with reactivity of the phenolics toward formaldehyde. Based on the calculated charges, estimates of the relative reactivity at each of the reactive sites on each of the phenolic compounds were determined. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 355–363, 2000     

Predicting the reactivity of phenolic compounds with formaldehyde. II. Continuation of an ab initio study

Phenol–formaldehyde resins are important adhesives used by the forest products industry. The phenolic compounds in these resins are derived primarily from petrochemical sources. Alternate sources of phenolic compounds include tannins, lignins, biomass pyrolysis products, and coal gasification products. Because of variations in their chemical structures, the reactivities of these phenolic compounds with formaldehyde vary in quite subtle ways. Previously, it was demonstrated that the reactivity of a number of phenols with formaldehyde in nonaqueous conditions could be correlated with charges calculated for reactive sites on the aromatic ring (Conner, A. H. J Appl Polym Sci 2000, 78, 355–363). We studied the reactivity of a larger number of phenolic compounds with formaldehyde in an aqueous solution using sodium hydroxide as the catalyst. Reaction rates were determined from measurements of the concentrations of the phenolic compounds and formaldehyde as functions of time. The reaction rate constants varied over a wide range (approximately 10^?2 to 10⁴ L mol^?1 h^?1). An estimate of the reactivity per reactive site on the phenolic ring was determined by dividing the rate by the number of reactive sites. Atomic charges for each phenolic compound were calculated by ab initio methods at the RHF/6‐31+ G level of theory using the CHelpG method. The charge per reactive site was estimated by summing the charges at all the reactive sites on the phenolic ring and dividing by the number of reactive sites. A strong correlation was observed between the reactivity per reactive site and the average charge per reactive site. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 135–140, 2002     

Comparison of free energy surfaces calculations from ab initio molecular dynamic simulations at the example of two transition metal catalyzed reactions

We carried out ab initio molecular dynamic simulations in order to determine the free energy surfaces of two selected reactions including solvents, namely a rearrangement of a ruthenium oxoester in water and a carbon dioxide addition to a palladium complex in carbon dioxide. For the latter reaction we also investigated the gas phase reaction in order to take solvent effects into account. We used two techniques to reconstruct the free energy surfaces: thermodynamic integration and metadynamics. Furthermore, we gave a reasonable error estimation of the computed free energy surface. We calculated a reaction barrier of ΔF = 59.5 ± 8.5 kJ mol(-1) for the rearrangement of a ruthenium oxoester in water from thermodynamic integration. For the carbon dioxide addition to the palladium complex in carbon dioxide we found a ΔF = 44.9 ± 3.3 kJ mol(-1) from metadynamics simulations with one collective variable. The investigation of the same reactions in the gas phase resulted in ΔF = 24.9 ± 6.7 kJ mol(-1) from thermodynamic integration, in ΔF = 26.7 ± 2.3 kJ mol(-1) from metadynamics simulations with one collective variable, and in ΔF = 27.1 ± 5.9 kJ mol(-1) from metadynamics simulations with two collective variables.     

Theoretical estimation of the apparent rate constants for ozone decomposition in gas and aqueous phases using ab initio calculations

An ab initio study, using the coupled cluster calculations (CCSD) method was conducted to investigate the kinetics of the ozone degradation in gas and aqueous phases considering the reaction of ozone with the hydroperoxyl radical. Two potential transition state paths, oxygen and hydrogen transfer, are studied and compared. It was revealed by the ab initio quantum chemical calculations that the calculated overall rate constant in the gas phase differs by approximately an order of magnitude from measured values. However, the calculated selectivity (branching fraction), which was measured directly with isotope studies of hydrogen atom transfer, is almost exactly equal to the experimental value at 298.15 K. The sensitivity analysis showed that adding the reaction between ozone and hydroperoxyl radical to the kinetic model accelerates the decomposition process by more than four times in the aqueous phase (pH = 7–8.5), and for an order of magnitude change in the rate constant of this reaction, the decomposition half-life changes by 20–45 %. This result might affect our understanding of atmospheric ozone chemistry.     

Theoretical conformational study of 1,1,1-trifluoro-4-mercapto-but-3-ene-2-thione and the importance of intramolecular hydrogen bonding in ground and first electronic excited state

Quantum chemical calculations of energies, geometrical structure, intramolecular hydrogen bonding (HB) and vibrational frequencies of 1,1,1-trifluoro-4-mercapto-but-3-ene-2-thione were carried out by the ab initio Hartree–Fock, Moller–Plesset second-order perturbation (MP2) and density functional theory (DFT) methods with 6-311++G** basis set in gas phase and water solution. The nature of the intramolecular hydrogen bond in the most stable chelated conformers has been studied by using the atoms in molecules theory of Bader, which is based on topological properties of the electron density. Natural bond orbital (NBO) analysis was also performed for better understanding of the nature of intramolecular interactions. The influence of the solvent on the stability order of conformers and the strength of intramolecular HB was considered using Tomasi's polarized continuum model. The HOMA, NICS, PDI, ATI, FLU and FLU _π indices as well-established aromaticity indicators are examined. The excited-state properties of intramolecular HB in hydrogen-bonded systems have been investigated theoretically using the time-dependent DFT method. The calculated highest occupied molecular orbital (MO) and lowest unoccupied MO with frontier orbital gap are presented. Further verification of the obtained transition state structures was implemented via intrinsic reaction coordinate analysis.     

An experimental and theoretical study on the effects of amine chain length on CO2 absorption performance

To explore the effect of amine chain length on CO₂ absorption performance, the reaction kinetics of CO₂ absorption in aqueous 1-dimethylamino-2-propanol (DMA2P), 1-diethylamino-2-propanol (DEA2P), 2-(methylamino)ethanol (MAE), and 2-(ethylamino)ethanol (EAE) solutions with different concentrations were explored using the stopped-flow apparatus. Additionally, Density Functional Theory (DFT) calculations were conducted to examine the reaction mechanism and the free energy barrier of the elementary reactions underlying CO₂ absorption in these four aqueous amine solutions. Kinetic models for CO₂ absorption in tertiary amines and secondary amines were established, based on the base-catalyzed hydration mechanism and the zwitterion mechanism, respectively, both of which perform well in predicting the relationship between k₀ and the amine concentration. The free energy barrier obtained by DFT is consistent with the activation energy barrier trend obtained by experiment. In addition, the effect of chain length on the free energy barrier was investigated through the chemical bond and weak interaction analysis.     

An experimental/computational study of steric hindrance effects on CO2 absorption in (non)aqueous amine solutions

The reaction kinetics and molecular mechanisms of CO₂ absorption using nonaqueous and aqueous monoethanolamine (MEA)/methyldiethanolamine (MDEA)/2-amino-2-methy-1-propanol (AMP) solutions were analyzed by the stopped-flow technique and ab initio molecular dynamics (AIMD) simulations. Pseudo first-order rate constants (k₀) of reactions between CO₂ and amines were measured. A kinetic model was proposed to correlate the k₀ to the amine concentration, and was proved to perform well for predicting the relationship between k₀ and the amine concentration. The experimental results showed that AMP/MDEA only took part in the deprotonation of MEA-zwitterion in nonaqueous MEA + AMP/MEA + MDEA solutions. In aqueous solutions, AMP can also react with CO₂ through base-catalyzed hydration mechanism beside the zwitterion mechanism. Molecular mechanisms of CO₂ absorption were also explored by AIMD simulations coupled with metadynamics sampling. The predicted free-energy barriers of key elementary reactions verified the kinetic model and demonstrated the different molecular mechanisms for the reaction between CO₂ and AMP.     

全氟三乙胺热解机理的实验与理论研究

氟胺类物质是最有希望作为哈龙替代品的含氮化合物之一,全氟三乙胺作为典型的氟胺类物质具有良好的灭火效果。为研究全氟三乙胺热解机理,在管式加热炉内对全氟三乙胺进行热分解,通过GC-MS分析全氟三乙胺在不同温度条件下的热解产物,并用Gaussian软件对其热解反应路径进行理论计算。结果表明：保持停留时间为10 s,全氟三乙胺的初始热解温度为600℃,750℃完全热解,热解产物有C₄F₉N、C₃F₇N、C₂F₆和C₃F₈,热解温度较低时C₄F₉N体积分数最大,热解温度较高时C₃F₇N体积分数最大。在全氟三乙胺热解反应路径计算中,全氟三乙胺分子中的C—C键断裂后存在1条反应路径,可生成实验产物中的C₃F₈;全氟三乙胺分子的C—N键断裂后存在3条反应路径,可生成实验产物中的C₃F₇N、 C₄F₉N和C₂F₆。全氟三乙胺热解后产生的CF₃自由基可与H、OH自由基发生反应,从而产生灭火作用。此外,其热解产物C₄F₉N和C₃F₇N具有CN双键,更容易与燃烧活泼自由基·OH、·H发生化学作用,对研究全氟三乙胺的灭火机理具有十分重要的意义。     

全氟三乙胺热解机理的实验与理论研究

氟胺类物质是最有希望作为哈龙替代品的含氮化合物之一,全氟三乙胺作为典型的氟胺类物质具有良好的灭火效果。为研究全氟三乙胺热解机理,在管式加热炉内对全氟三乙胺进行热分解,通过GC-MS分析全氟三乙胺在不同温度条件下的热解产物,并用Gaussian软件对其热解反应路径进行理论计算。结果表明：保持停留时间为10 s,全氟三乙胺的初始热解温度为600℃,750℃完全热解,热解产物有C₄F₉N、C₃F₇N、C₂F₆和C₃F₈,热解温度较低时C₄F₉N体积分数最大,热解温度较高时C₃F₇N体积分数最大。在全氟三乙胺热解反应路径计算中,全氟三乙胺分子中的C—C键断裂后存在1条反应路径,可生成实验产物中的C₃F₈;全氟三乙胺分子的C—N键断裂后存在3条反应路径,可生成实验产物中的C₃F₇N、 C₄F₉N和C₂F₆。全氟三乙胺热解后产生的CF₃自由基可与H、OH自由基发生反应,从而产生灭火作用。此外,其热解产物C₄F₉N和C₃F₇N具有CN双键,更容易与燃烧活泼自由基·OH、·H发生化学作用,对研究全氟三乙胺的灭火机理具有十分重要的意义。     

Experimental and theoretical study on the structural,electrical and optical properties of tantalum-doped ZnO nanoparticles prepared via sol-gel acetate route

Pure and Ta-doped ZnO were prepared by the sol-gel method in acetic medium using different annealing temperature treatments. The effects of low Ta doping on the crystallinity and electrical properties of ZnO nanoparticles were analyzed by means of X-ray diffraction and micro-Raman, UV–visible, and impedance spectroscopies.We also performed first principles calculations in order to study the predicted changes in the structural, vibrational and electronic properties induced by the inclusion of the impurities, and to complement the experimental measurements.We showed that above thermal treatments at 600 °C the precursor samples take the hexagonal wurtzite ZnO phase with high crystallinity. For the doped samples, we found that the synthesizing method has good Ta doping efficiency of the ZnO host structure. Also, Ta doping substantially decreases the resistivity compared to pure ZnO. These results confirm that Ta impurities can substitute Zn atoms and act as donor impurities in the host semiconductor.     

Foaming of polymers with supercritical CO2: An experimental and theoretical study

Microcellular polystyrene (PS) foams and porous structures of the biodegradable poly(d,l-lactic acid) (P_d,lLA) were prepared with the batch foaming technique (pressure quench) using supercritical CO₂ as blowing agent. The effect of pressure, temperature and depressurization rate on the final porous structure was investigated. The results revealed that the size of the pores decreases and their population density increases with pressure increase, or decrease of temperature, and/or increase of the depressurization rate. The results were correlated by combining nucleation theory with NRHB model in order to account for and emphasize the physical mechanism related to nucleation of bubbles inside the supersaturated polymer matrix. A satisfactory agreement between correlations and experimental data was obtained indicating that the nucleation theory yields quantitative correlations when variables such as sorption, degree of plasticization, and surface tension of the system polymer-supercritical fluid are accurately described.     

Influence of size and shape on optical properties of cesium tungsten bronze: An experimental and theoretical approach

Although the optical properties of nanocrystalline cesium tungsten bronze have been widely studied, there is a lack of research on the effect of particle size on its optical properties. In order to further investigate size and shape effect on the NIR shielding performance, cesium tungsten bronze nanoparticles with different sizes and morphologies were prepared by two methods. The size of irregular shaped samples prepared by solvothermal method is tens of nanometers, while the size of hexagonal prism shaped samples prepared by solid state reaction method is hundreds of nanometers. The element spectrums shows that there are more oxygen vacancies in large particles than in small particles. The NIR shielding performance of large particles far lower than that of small particles, indicating that the influence of shape and size on optical properties is more obvious than that of oxygen vacancy. Theoretical calculation on hexagonal prism shaped particles exhibits that the NIR extinction of large aspect ratio is better at longer wavelength and small aspect ratio is better at shorter wavelength.     

Understanding the atomic and electronic origin of mechanical property in thaumasite and ettringite mineral crystals

Ettringite and thaumasite are 2 of the relevant secondary products in portland cement minerals. They are rare crystals with high water content. Two density functional theory based ab initio packages VASP and the OLCAO were used for exploring the geometry structure, electronic, and mechanical properties of ettringite and thaumasite. The calculations focus on the comparison of their structures and properties to gain insights that can reveal the minute difference in properties due to differences in their structure, composition and water content. Detailed analysis of interatomic bonding shows the similarities and subtle difference between them even though thaumasite has the Si tetrahedron as the backbone unit in contrast to ettringite with Al‐columns and no Si atoms. Moreover, thaumasite has strong C–O bonds that are absent in ettringite, and ettringite has far more water molecules with a substantial contribution from the hydrogen bonding. It is shown that the role played by relatively strong S–O bonds in both crystals has a large impact on the hydration in these crystals. On the basis of calculated total bond order density, it is concluded that thaumasite is slightly more cohesive than ettringite consistent with the calculated mechanical properties. The detailed comparative results for these 2 important minerals we obtained in this paper, many of them for the first time, will pave the way to understanding the structure and electronic structure origin of other more complex cement crystals.     

An experimental and theoretical study of the nitrosation of ammonia and thiourea

The nitrosation reactions of both thiourea and ammonia have been investigated, owing to their interesting kinetic behaviour and their industrial importance in the sensitisation of emulsion explosives. Kinetic experiments were conducted using a well-mixed aqueous reactor, from which samples were periodically removed, quenched, and then analysed for nitrite concentration using ion chromatography. We derived a number of plausible rate equations for both the ammonia and thiourea gassing processes, which we subsequently tested against experimental results to determine the operating kinetic mechanism, under a range of conditions. The reaction between ammonia and nitrite was seen to proceed by way of the nitrosating agent dinitrogen trioxide. In the presence of thiocyanate, however, dinitrogen trioxide was replaced by the thermodynamically more powerful nitrosating agent nitrosyl thiocyanate. Both reaction mechanisms exhibited relatively similar temperature dependencies, with respective activation energies of 56 and , determined between 25 and 45 °C, indicating reaction-controlled regimes. The effects of pH, temperature and ammonium nitrate concentration on the rate of thiourea nitrosation were studied. The rate of reaction was independent of ammonium nitrate concentration, while decreasing the pH of the reaction medium resulted in significant increases in the rate of reaction. The activation energy was evaluated as being in the temperature range of 25 to 45 °C. Theoretical evidence at the G2MP2 level of theory supports a mechanism of thiourea nitrosation involving rapid deprotonation of S-nitrosothiourea, followed by rate-limiting S to N migration of the nitroso group.     

An experimental and theoretical study on the initial period of cake filtration

Experimental measurements were made of the average specific cake resistance during the initial period of cake filtration, and the theoretical calculations about the period were also performed. The “filtration-permeation method” in the filtration cell of small area was used to measure the flow rate during the initial period of filtration, which is essentially characterized by the large flux due to fast flow rate and the rapid change of flow rate within a relatively short time interval. The measured average specific cake resistances of thin cakes which represent the cakes of initial period had very large values compared to the overall average specific cake resistance. This experimental result was contrary to the conventional theory about the initial period. Applying the “unified theory on solid-liquid separation” to the initial period, the average specific cake resistances at the initial period can have the large values--more than two times greater than that of the overall value.     

Electronic structures and molecular properties of FLBDOB and its derivatives: A combined experimental and theoretical study

Theoretical studies on a new unsymmetrical electrolyte salt, lithium [3-fluoro-1,2-benzenediolato(2-)-o,o′ oxalato]borate (FLBDOB), and its derivatives, lithium bis[3-fluoro-1,2-benzenediolato(2-)-o,o]borate (FLBBB), and lithium bis(oxalate)borate (LBOB) are carried out using density functional theory (DFT) method and B3LYP theory level. Bidentate structures involving two oxygen atoms are preferred. Based on these conformations, a linear correlation is observed between the highest occupied molecular orbital (HOMO) energies and the limiting oxidation potentials measured by linear sweep voltammetry, which supports experimental results that strongly electron-withdrawing substituent anions are more resistant against oxidation. The correlations are also observed between ionic conductivity and binding energy, solubility and theoretical set of parameters of anion, thermal stability and the hardness (η). Wave function analyses are performed by natural bond orbital (NBO) method to further investigate the cation-anion interactions.     

Enhanced thermoelectric properties of Cu2Se via Sb doping: An experimental and computational study

In this study, Cu₂Se_1?xSb_x (x = 0.000, 0.005, 0.010, and 0.015) thermoelectric materials were synthesised using a solid-state reaction technique. A first-principles calculation indicated that the formation energy of the substitution of antimony (Sb) on the Se site is negative and more stable than those of copper (Cu) sites. Sb doping enhanced the lamellar orientation, decreased the grain size, and created an acceptor impurity level. The electrical resistivity and Seebeck coefficient decreased with increasing Sb doping. A minimum reduction in the thermal conductivity by approximately three times that of the undoped sample was obtained at x = 0.005 with a value of 0.40 W/m K at 523 K. The maximum figure of merit (ZT) was obtained at x = 0.005 with a value of 0.47 at 523 K. These findings indicate that substituting Sb into Se sites is an efficient approach for improving copper selenide (Cu₂Se) thermoelectric materials.     

An experimental and theoretical study on the photocatalytic antibacterial activity of boron-doped TiO2 nanoparticles

Boron-doped titanium dioxide nanoparticles (B–TiO₂ NPs) were prepared by a sol-gel method. The physicochemical properties of B–TiO₂ NPs were characterized by X-ray diffraction, transmission electron microscopy, ultraviolet–visible diffuse reflectance spectroscopy and photoluminescence spectroscopy. The band structure and electrical properties of B–TiO₂ NPs were investigated using the first-principle. The effects of the concentration gradient of doping B ions on the photocatalytic antibacterial activity of B–TiO₂ NPs under visible-light irradiation were investigated by the inhibition zone method and the shaking flask method. The experimental results show that B–TiO₂ NPs are mainly composed of the anatase phase, but no B-related phase was observed. With the increase of the doping amount of boron ions, the particle size decreases and the specific surface area increases. B atoms mainly exist in the form of substitutional dopant and interstitial dopant. Theoretical calculations reveal that B atoms in the TiO₂ matrix exist much more easily as interstitial dopant, but B–TiO₂ NPs composed of B substituted dopant have better photocatalytic performance. The results of the antibacterial assays show that B–TiO₂ NPs have strong antibacterial activities and some bactericidal activities. Finally, the mechanism of the antibacterial activity of B–TiO₂ NPs are examined.     

Insights into the confinement effect on isobutane alkylation with C4 olefin catalyzed by zeolite catalyst: A combined theoretical and experimental study

Elucidating the confinement effect harbours tremendous significance for isobutane alkylation with C₄ olefin. Herein, the confinement effect over zeolite catalysts was elucidated by combining DFT calculations, experiments(using the novel Beta zeolite exposing only external surfaces(Beta-E) and conventional Beta-I zeolite with both external and internal surfaces) and multi-techniques(e.g., TGA-DTG,HRTEM, SEM and XRD). It is found that the main active sites for C₄ alkylation r...