The reaction mechanism and interfacial crystallization of Al nanoparticle-embedded Ni under shock loading

The shock-induced reaction mechanism and characteristics of Ni/Al system,considering an Al nanoparticle-embedded Ni single crystal,are investigated through molecular dynamics simulation.For the shock melting of Al nanoparticle,interfacial crystallization and dissolution are the main characteristics.The reaction degree of Al particle first increases linearly and then logarithmically with time driven by rapid mechanical mixing and following dissolution.The reaction rate increases with the decrease of particle diameter,however,the reaction is seriously hindered by interfacial crystallization when the diameter is lower than 9 nm in our simulations.Meanwhile,we found a negative exponential growth in the fraction of crystallized Al atoms,and the crystallinity of B2-NiAl(up to 20%)is positively correlated with the specific surface area of Al particle.This can be attributed to the formation mechanism of B2-NiAl by structural evolution of finite mixing layer near the collapsed interface.For shock melting of both Al particle and Ni matrix,the liquid-liquid phase inter-diffusion is the main reaction mechanism that can be enhanced by the formation of internal jet.In addition,the enhanced diffusion is manifested in the logarithmic growth law of mean square displacement,which results in an almost constant reaction rate similar to the mechanical mixing process.

Study on trifluoromethanesulfonic acid-promoted synthesis of daidzein: Process optimization and reaction mechanism

Daidzein has been widely used in pharmaceuticals,nutraceuticals,cosmetics,feed additives,etc.Its preparation process and related reaction mechanism need to be further investigated.A cost-effective process for synthesizing daidzein was developed in this work.In this article,a two-step synthesis of daidzein(Friedel–Crafts acylation and[5+1]cyclization)was developed via the employment of trifluoromethanesulfonic acid(TfOH)as an effective promoting reagent.The effect of reaction conditions such as solvent,the amount of TfOH,reaction temperature,and reactant ratio on the conversion rate and the yield of the reaction,respectively,was systematically investigated,and daidzein was obtained in 74.0%isolated yield under optimal conditions.Due to the facilitating effect of TfOH,the Friedel–Crafts acylation was completed within 10 min at 90℃ and the[5+1]cyclization was completed within 180 min at 25℃.In addition,a possible reaction mechanism for this process was proposed.The results of the study may provide useful guidance for industrial production of daidzein on a large scale.

Cu-based materials for electrocatalytic CO_(2) to alcohols:Reaction mechanism,catalyst categories,and regulation strategies

Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.

Study of the reaction mechanism for preparing powdered activated coke with SO_(2)adsorption capability via one-step rapid activation method under flue gas atmosphere

In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.

Insights into kinetics and reaction mechanism of acid-catalyzed transesterification synthesis of diethyl oxalate

The catalytic performance of different acidic catalysts for diethyl oxalate synthesis from the one-step transesterification of dimethyl oxalate and ethanol was evaluated.The effects of different factors(e.g.,acidity,electron accepting capacity,cations type and crystalline water)on the catalytic activity of acidic catalysts were investigated respectively.It was proposed and confirmed that the transesterification reaction catalyzed by a Lewis acid(FeCl3)and a Bronsted acid(H2SO4)follows a first-order kinetic reaction process.In addition,the Lewis acid-catalyzed transesterification processes with different ester structures were used to further explore and understand the speculated reaction mechanism.This work enriches the theoretical understanding of acid-catalyzed transesterification reactions and is of great significance for the development of highly active catalysts for diethyl oxalate synthesis,diminishing the industrial production cost of diethyl oxalate,and developing downstream bulk or high-value-added industrial products.

Mechanism for thermite reactions of aluminum/iron-oxide nanocomposites based on residue analysis

Sol-gel method was employed to combine Al and iron-oxide to form nanocomposites （nano-Al/xero-Fe2O3 and micro-Al/xero-Fe2O3）. SEM, EDS and XRD analyses were used to characterize the nanocomposites and the results indicated that nano-Al and micro-Al were compactly wrapped by amorphous iron-oxide nanoparticles （about 20 nm）, respectively. The iron-oxide showed the mass ratio of Fe to O as similar as that in Fe2O3. Thermal analyses were performed on two nanocomposites, and four simple mixtures （nano-Al＋xero-Fe2O3, nano-Al＋micro-Fe2O3, micro-Al＋xero-Fe2O3, and micro-Al＋micro-Fe2O3） were also analyzed. There were not apparent distinctions in the reactions of thermites fueled by nano-Al. For thermites fueled by micro-Al, the DSC peak temperatures of micro-Al/Xero-Fe2O3 were advanced by 68.1 ℃ and 76.8 ℃ compared with micro-Al＋xero-Fe2O3 and micro-Al＋micro-Fe2O3, respectively. Four thermites, namely, nano-Al/xero-Fe2O3, nano-Al＋micro-Fe2O3, micro-Al/xero-Fe2O3, and micro-Al＋micro-Fe2O3, were heated from ambient temperature to 1020 ℃, during which the products at 660 ℃ and 1020 ℃ were collected and analyzed by XRD. Crystals of Fe, FeAl2O4, Fe3O4,α-Fe2O3, Al,γ-Fe2O3, Al2.667O4, FeO andα-Al2O3 were indexed in XRD patterns. For each thermite, according to the specific products, the possible equations were given. Based on the principle of the minimum free energy, the most reasonable equations were inferred from the possible reactions.

Reaction mechanisms of low-grade molybdenum concentrate during calcification roasting process

The effects of Ca-based additives on roasting properties of low-grade molybdenum concentrate were studied. The resultsshow that calcium-based additives can react with molybdenum concentrate to form CaSO4 and CaMoO4. The initial oxidationtemperature of MoS2 is 450℃, while the formation of CaMoO4 and CaSO4 occurs above 500℃. The whole calcification reactionsare nearly completed between 600 and 650℃. However, raising the temperature further helps for the formation of CaMoO4 but isdisadvantageous to sulfur fixing rate and molybdenum retention rate. Calcification efficiency of Ca-based additives follows theorder： Ca（OH）2〉CaO〉CaCO3. With increasing the dosage of Ca（OH）2, the molybdenum retention rate and sulfur-fixing rate rise, butexcessive dosages would consume more acid during leaching process. The appropriate mass ratio of Ca（OH）2 to molybdenumconcentrate is 1：1. When roasted at 650 ℃ for 90 min, the molybdenum retention rate and the sulfur-fixing rate of low-grademolybdenum concentrate reach 100% and 92.92%, respectively, and the dissolution rate of molybdenum achieves 99.12% withcalcines being leached by sulphuric acid.

Reaction mechanism of preparation of titanium by electro-deoxidation in molten salt

The electro-deoxidation of TiO2 was investigated in molten CaCl2.Back electromotive force measurements,constant voltage electrolytic experiments,contrast experiments of different cathodes,and cyclic voltammograms were carried out for solving the puzzle of reduction mechanism.The results showed that the reduction process proceeded step by step.TiO2 was first reduced to Ti3O5 or Ti2O3,and then further reduced to Ti3O,Ti2O,TiO and Ti.In addition,direct electrochemical reduction of titanium dioxide was the primary cathodic reaction;meanwhile,some calciothermic reduction reactions also happened at the cathode.Cyclic voltammograms of solid titanium dioxide and molybdenum wire in molten salts with different compositions were also studied.

Promotional roles of ZrO_2 and WO_3 in V_2O_5-WO_3/TiO_2-ZrO_2 catalysts for NO_x reduction by NH_3:Catalytic performance,morphology,and reaction mechanism

V2O5/TiO2-ZrO2 catalysts containing various amounts of WO3 were synthesized.The catalyst morphologies,catalytic performances,and reaction mechanisms in the selective catalytic reduction of NOx by NH3 were investigated using in situ diffuse-reflectance infrared Fourier-transform spectroscopy,temperature-programmed reduction（TPR）,X-ray diffraction,and the Brunauer-Emmett-Teller（BET） method.The BET surface area of the triple oxides increased with increasing ZrO2 doping but gradually decreased with increasing WO3 loading.Addition of sufficient WO3 helped to stabilize the pore structure and the combination of WO3 and ZrO2 improved dispersion of all the metal oxides.The mechanisms of reactions using V2O5-9%WO3/TiO2-ZrO2 and V2O5-9%WO3/TiO2were compared by using either a single or mixed gas feed and various pretreatments.The results suggest that both reactions followed the Eley-Ridel mechanism;however,the dominant acid sites,which depended on the addition of WO3 or ZrO2,determined the pathways for NOx reduction,and involved[NH4^＋-NO-Bronsted acid site]^＊ and[NH2-NO-Lewis acid site]^＊ intermediates,respectively.NH3-TPR and H2-TPR showed that the metal oxides in the catalysts were not reduced by NH3 and O2did not reoxidize the catalyst surfaces but participated in the formation of H2O and NO2.

Density Functional Theory Study of Mechanism of Cycloaddition Reaction Between Dimethyl-Silylene Carbene and Acetone

The mechanism of the cycloaddition reaction between singlet dimethyl-silylene carbene and acetone has been investigated with density functional theory, From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The presented rule of this reaction： the [2＋2] cycloaddition effect between the πorbital of dimethyl-silylene carbene and the π orbital of π-bonded compounds leads to the formation of a twisty four-membered ring intermediate and a planar four-membered ring product; The unsaturated property of C atom from carbene in the planar four-membered ring product,resulting in the generation of CH3-transfer product and silicic bis-heterocyclic compound.

Changing the balance of the MTO reaction dual-cycle mechanism: Reactions over ZSM-5 with varying contact times

The methanol to olefins （MTO） reaction was performed over ZSM‐5 zeolite at 300℃ under various methanol weight hourly space velocity （WHSV） values. During these trials, the catalytic perfor‐mance was assessed, in addition to the formation and function of organic compounds retained in the zeolite. Analysis of reaction effluents and confined organics demonstrated a dual‐cycle reaction mechanism when employing ZSM‐5. The extent of the hydrogen transfer reaction, a secondary reac‐tion in the MTO process, varied as the catalyst‐methanol contact time was changed. In addition, 12C/13C‐methanol switch experiments indicated a relationship between the dual‐cycle mechanism and the extent of the hydrogen transfer reaction. Reactions employing a low methanol WHSV in conjunction with a long contact time favored the hydrogen transfer reaction to give alkene products and promoted the generation and accumulation of retained organic species, such as aromatics and methylcyclopentadienes, which enhance the aromatic cycle. When using higher WHSV values, the reduced contact times lessened the extent of the hydrogen transfer reaction and limited the genera‐tion of methylcyclopentadienes and aromatic species. This suppressed the aromatic cycle, such that the alkene cycle became the dominant route during the MTO reaction.

Theoretical Study on Mechanism and Kinetics of Reaction of O（^3p） with Propane

The reaction of C3H8＋O（^3p）→C3HT＋OH is investigated using ab initio calculation and dynamical methods. Electronic structure calculations for all stationary points are obtained using a dual-level strategy. The geometry optimization is performed using the unrestricted second-order Moller-Plesset perturbation method and the single-point energy is computed us- ing the coupled-cluster singles and doubles augmented by a perturbative treatment of triple excitations method. Results indicate that the main reaction channel is C3Hs＋O（^3p）→i- C3HT＋OH. Based upon the ab initio data, thermal rate constants are calculated using the variational transition state theory method with the temperature ranging from 298 K to 1000 K. These calculated rate constants are in better agreement with experiments than those reported in previous theoretical studies, and the branching ratios of the reaction are also calculated in the present work. Furthermore, the isotope effects of the title reaction are calculated and discussed. The present work reveals the reaction mechanism of hydrogenabstraction from propane involving reaction channel competitions is helpful for the understanding of propane combustion.

Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

TDDFT Study on Different Sensing Mechanisms of Similar Cyanide Sensors Based on Michael Addition Reaction

The solvents and substituents of two similar fluorescent sensors for cyanide, 7-diethylamino- 3-formylcoumarin （sensor a） and 7-diethylamino-3-（2-nitrovinyl）coumarin （sensor b）, are proposed to account for their distinct sensing mechanisms and experimental phenomena. The time-dependent density functional theory has been applied to investigate the ground states and the first singlet excited electronic states of the sensor as well as their possible Michael reaction products with cyanide, with a view to monitoring their geometries and photophysieal properties. The theoretical study indicates that the protic water solvent could lead to final Michael addition product of sensor a in the ground state, while the aprotic acetonitrile solvent could lead to carbanion as the final product of sensor b. Furthermore, the Michael reaction product of sensor a has been proved to have a torsion structure in its first singlet excited state. Correspondingly, sensor b also has a torsion structure around the nitrovinyl moiety in its first singlet excited state, while not in its carbanion structure. This could explain the observed strong fluorescence for sensor a and the quenching fluorescence for the sensor b upon the addition of the cyanide anions in the relevant sensing mechanisms.

Extracting reaction mechanism analysis of Zn and Si from zinc oxide ore by NaOH roasting method

The orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore with NaOH aiming to comprehensively utilize zinc oxide ore.The optimized reaction conditions were molar ratio of NaOH to zinc oxide ore 6:1,roasting temperature 450°C,holding time 150 min.The molar ratio of NaOH to zinc oxide ore was the most predominant factor affecting the extraction ratios of zinc oxide and silica.The mineral phase transformations were investigated by testing the phases of specimens obtained at different temperatures.The process was that silica reacted with molten NaOH to form Na_2SiO_3 at first,then transformed into Na_4SiO_4 with temperature rising.ZnCO_3 and its decomposing product ZnO reacted with NaOH to form Na_2ZnO_2.Na_2ZnSiO_4was also obtained.The reaction rate was investigated using unreacted shrinking core model.Two models used were chemical reaction at the particle surface and diffusion through the product layer.The results indicated that the reaction rate was combine-controlled by two models.The activation energy and frequency factor were obtained as 24.12 k J/mol and 0.0682,respectively.

Theoretical Studies on Reaction Mechanisms of HNCS with NH(X^3Σ)

The reaction mechanisms of HNCS with NH（X^3∑ ） were theoretically investigated. The minimum energy paths （MEP） of the reaction were calculated by using the density functional theory（DFT） at the B3LYP/6-311 ＋ ＋ G^＊＊ level. The equilibrium structural parameters, the harmonic vibrational frequencies, the total energies, and the zeropoint energies（ZPE） of all the species were calculated. The single-point energies along the MEP were further refined at the QCISD（T）/6-311 ＋ ＋ G^＊ ＊ level. It was found that the mechanisms of the HNCS ＋ NH（X^3∑） reaction involve two channels producing the HNC ＋ HNS and the N2H2 ＋ CS products. Channel 1 plays a dominant role and the HNC ＋ HNS are the main preduets. The reaction is exothermie.

Identification of relevant active sites and a mechanism study for reverse water gas shift reaction over Pt/CeO_2 catalysts

Reverse water gas shift (RWGS) reaction can serve as a pivotal stage in the CO2 conversion processes, which is vital for the utilization of CO2. In this study, RWGS reaction was performed over Pt/CeO2 catalysts at the temperature range of 200-500 degrees C under ambient pressure. Compared with pure CeO2, Pt/CeO2 catalysts exhibited superior RWGS activity at lower reaction temperature. Meanwhile, the calculated TOF and E-a values are approximately the same over these Pt/CeO2 catalysts pretreated under various calcination conditions, indicating that the RWGS reaction is not affected by the morphologies of anchored Pt nanoparticles or the primary crystallinity of CeO2. TPR and XPS results indicated that the incorporation of Pt promoted the reducibility of CeO2 support and remarkably increased the content of Ce 3 + sites on the catalyst surface. Furthermore, the CO TPSR-MS signal under the condition of pure CO2 flow over Pt/CeO 2 catalyst is far lower than that under the condition of adsorbed CO2 with H-2 -assisted flow, revealing that CO2 molecules adsorbed on Ce3+ active sites have difficult in generating CO directly. Meanwhile, the adsorbed CO2 with the assistance of H-2 can form formate species easily over Ce3+ active sites and then decompose into Ce3+-CO species for CO production, which was identified by in-situ FTIR. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B. V. and Science Press. All rights reserved.

Cathodic reaction mechanisms in CO2 corrosion of low-Cr steels

The cathodic reaction mechanisms in CO2 corrosion of low-Cr steels were investigated by potentiodynamic polarization and galvanostatic measurements.Distinct but different dominant cathodic reactions were observed at different p H levels.At the higher p H level(p H>~5),H2 CO3 reduction was the dominant cathodic reaction.The reaction was under activation control.At the lower pH level(pH<~3.5),H+reduction became the dominant one and the reaction was under diffusion control.In the intermediate area,there was a transition region leading from one cathodic reaction to another.The measured electrochemical impedance spectrum corresponded to the proposed cathodic reaction mechanisms.

Reaction Mechanism,Synthesis and Characterization of Urea-glyoxal(UG) Resin

The reaction mechanism of glyoxal （G） with urea （U） under weak acid condition was theoretically investigated at PW91/DNP/COSMO of quantum chemistry using density functional theory （DFT） method. The results show that the addition reaction of G with U under the conditions mainly involves the reactions of U with protonated glyoxal （p-G）, protonated 2,2-dihy- droxyacetaldehyde （p-G 1） and protonated bis-hemdiol （p-G2） to form two important carbocation reactive intermediates of C-p-UG and C-p-UG1, and two important hydroxyl compounds of UG and UG1. These compounds play important roles in the formation of UG resin. According to the result of quantum chemical calculation, UG resin was synthesized successfully under weak acid conditions. The UG resin was characterized by matrix assisted laser desorption ionization time of flight mass spectrometry （MALDI-TOF-MS）, ultraviolet and visible spectroscopy （UV-vis）, Fourier transform infrared spectroscopy （FT1R） and nuclear magnetic resonance spectroscopy （13CNMR and 1HNMR）. These instrumental analytical results agree with each other and further confirm the addition reaction pathway of glyoxal with urea proposed by quantum chemical calculation.

In situ reaction mechanism of MgAlON in Al–Al2O3–MgO composites at 1700°C under flowing N2

The Al–AlO–MgO composites with added aluminum contents of approximately 0wt%, 5wt%, and 10wt%, named as M, M, and M, respectively, were prepared at 1700°C for 5 h under a flowing Natmosphere using the reaction sintering method. After sintering, the Al–AlO–MgO composites were characterized and analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results show that specimen Mwas composed of MgO and MgAlO. Compared with specimen M, specimens Mand Mpossessed MgAlON, and its production increased with increasing aluminum addition. Under an Natmosphere, MgO, AlO, and Al in the matrix of specimens Mand Mreacted to form MgAlON and AlN-polytypoids, which combined the particles and the matrix together and imparted the Al–AlO–MgO composites with a dense structure. The mechanism of MgAlON synthesis is described as follows. Under an Natmosphere, the partial pressure of oxygen is quite low; thus, when the Al–AlO–MgO composites were soaked at 580°C for an extended period, aluminum metal was transformed into AlN. With increasing temperature, AlOdiffused into AlN crystal lattices and formed AlN-polytypoids; however, MgO reacted with AlOto form MgAlO. When the temperature was greater than(1640 ± 10)°C, AlN diffused into AlOand formed spinel-structured AlON. In situ MgAlON was acquired through a solid-solution reaction between AlON and Mg AlOat high temperatures because of their similar spinel structures.