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.

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.

Mechanism Study of BF_(3)/n-Butanol-catalyzed 1-Decene Oligomerization Reaction

The active catalysts of the BF_(3)/n-C_(4)H_(9)OH-catalyzed 1-decene oligomerization reaction,as well as the distribution of the reaction products,was investigated by molecular simulation.The calculation results show that(BF_(3))_(2)·n-C_(4)H_(9)OH catalyzes the 1-decene oligomerization reaction with higher activity compared to BF_(3)·n-C_(4)H_(9)OH,which is the most catalytically active substance in the BF_(3)/n-C_(4)H_(9)OH catalyst system.The reaction energy barriers and heats of reaction of chain initiation,chain growth,and chain termination in BF_(3)/n-C_(4)H_(9)OH-catalyzed 1-decene oligomerization are calculated to reveal the product distribution.The calculation results show that the contents of the oligomerization reaction products in descending order are trimer,tetramer,pentamer,and dimer.The calculated results were consistent with the experimentally obtained product distribution.

In situ infrared, Raman and X-ray spectroscopy for the mechanistic understanding of hydrogen evolution reaction

Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.

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.

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.

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.

Study on the Reaction Mechanism of Naphthalene with Oxalyl Chloride

The reaction of naphthalene with oxalyl chloride in the presence of anhydrous AlCl3 was investigated. The homolog of dinaphthyl methanone can be obtained mainly from this reaction. Naphthalene conversion does not have evident correlation with the amount of AlCl3. The results show that the reaction proceeds via carbon cation electrophilic substitution reaction-free radical substitution reaction pathway.

Anode reaction mechanisms of Na|NaCl-CaCl2|Zn liquid metal battery

Na|NaCl-CaCl_(2)|Zn liquid metal battery is regarded as a promising energy storage system for power grids.Despite intensive attempts to present a real mechanism of metal electrodes reaction, those for Na||Zn LMBs are not clear yet. Herein, the anode reactions for the multiple discharge potential plateaus were deduced by means of FactSage thermochemical software, which were subsequently validated by X-ray diffraction analysis and the modeling of phase transformation in the cooling process. A pre-treatment process was proposed for the analysis of anode product composition using the atomic absorption spectrometry method, and the anode states at working temperature(560 ℃) were obtained by the Na-CaZn ternary phase for the first time. The results indicate the discharge of Na and Ca led to the formation of Ca-Zn intermetallic compounds, whilst the extraction of Ca in Ca-Zn intermetallic compounds was responsible for the multiple discharge plateaus. Moreover, it was found that the charging product was in electrochemical double liquid metal layers, which are composed of Na and Ca with dissolved Zn respectively.

Unraveling the reaction mechanism of low dose Mn dopant in Ni(OH)_(2) supercapacitor electrode

Mn doping is deemed as a promising strategy to improve the electrochemical performance of the a-Ni(OH)_(2)battery-type supercapacitor electrode.However,the internal structure evolution,the pathways and the dynamics of the proton/intercalated anion migration,as well as the functioning mechanism of Mn dopant to stabilize the layered structure during cycles remain unclear.Here,we unveil that irreversible oxidization of Mn^(3+)at the initial CV cycles,which will remain as Mn^(4+)in the NiO_(2)slabs after the first oxidization to effectively suppress the phase transformation fromα-Ni(OH)_(2)/γ-NiOOH toβ-Ni(OH)_(2)/β-NiOOH and further maintain the structural integrity of electrode.With a synergistic combination of theoretical calculations and various structural probes including XRD and^(2)H MAS solid state NMR,we decode the structure evolution and dynamics in the initial CV(cyclic voltammetry)cycles,including the absorption/desorption of hydrogen containing species,migration of intercalated anions/water molecules and the change of interlayer space.This present work elucidates a close relationship between doping chemistry and structural reliability,paving a novel way of reengineering supercapacitor electrode materials.

Preparation of Polystyrenylphosphonous Acid of Low Polymerization Degree and Influence of Initiators upon the Free Radical Reaction Mechanism

The polystyrenylphosphonous acid (PSPA) of low polymerization degree was prepared with one step reaction. The reaction mechanism was changed with different initiators. For the reaction with AIBN or BPO as the initiator, there are 2 or 3 series of radical reaction chains and 5 or 9 series of polystyrenyl products. The main products are PSPA without or with the fragment of the initiator H[CH(C6H5)-CH2]n-PO2H2 and C6H5CO2-[CH2CH (C6H5)]n-PO2H2 respectively.

Porous core–shell CoMn_2O_4 microspheres as anode of lithium ion battery with excellent performances and their conversion reaction mechanism investigated by XAFS

Porous core-shell CoMn204 microspheres of ca. 3-5μm in diameter were synthesized and served as an-ode of lithium ion battery. Results demonstrate that the as-synthesized CoMn204 materials exhibit excel-lent electrochemical properties. The CoMn204 anode can deliver a large capacity of 1070 mAh g-1 in thefirst discharge, a reversible capacity of 500 mAh g^-1 after 100 cycles with a coulombic efficiency of 98.5% at a charge-discharge current density of 200 mA g^-l, and a specific capacity of 385 mAh g^-1 at a muchhigher charge-discharge current density of 1600mA g^-1. Synchrotron X-ray absorption fine structure（XAFS） techniques were applied to investigate the conversion reaction mechanism of the CoMn204 anode.The X-ray absorption near edge structure （XANES） spectra revealed that, in the first discharge-charge cy-cle, Co and Mn in CoMn204 were reduced to metallic Co and Mn when the electrode was discharged to0.01 V, while they were oxidized respectively to CoO and MnO when the electrode was charged to 3.0V.Experiments of both XANE5 and extended X-ray absorption fine structure （EXAFS） revealed that neithervalence evolution nor phase transition of the porous core-shell CoMn204 microspheres could happen inthe discharge plateau from 0.8 to 0.6V, which demonstrates the formation of solid electrolyte interface（SEI） on the anode.

Theoretical Study of the AlCl Disproportionation Reaction Mechanism on the Al(100) Surface

The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum （100） surfaces has been investigated by the plane-wave density functional theory （DFT）. Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum （100） surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step ofAlCl disproportionation reaction on the aluminum （100） surfaces.

Ab Initio Study on the Mechanism of Cycloaddition Reaction between Silylene Carbene (H_2Si=C:) and Acetone

The mechanism of cycloaddition reaction between singlet silylene carbene and acetone has been investigated with CCSD（T）//MP2/6-31G method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. One consists of two steps： （1） the two reactants （R1, R2） firstly form a four-membered ring intermediate （INT4） through a barrier-free exothermic reaction of 585.9 kJ/mol; （2） Then intermediate （INT4） isomerizes to CH3-transfer product （P4.1） via a transition state （TS4.1） with energy barrier of 5.3 kJ/mol. The other is as follows： on the basis of intermediate （INT4） created between R1 and R2, intermediate （INT4） further reacts with acetone （R2） to form the intermediate （INT5） through a barrier-free exothermic reaction of 166.3 kJ/mol; Then, intermediate （INT5） isomerizes to a silicic bis-heterocyclic product （P5） via a transition state （TS5）, for which the barrier is 54.9 kJ/mol. The presented rule of this reaction： the [2＋2] cycloaddition effect between the π orbital of silylene carbene and the π orbital of π-bonded compounds leads to the formation of a four-membered ring intermediate （INT4）; The unsaturated property of C atom from carbene in the four-membered ring intermediate （INT4） results in the generation of CH3-transfer product （P4.1） and silicic bis-heterocyclic compound （P5）.

Reaction mechanism and kinetics of pressurized pyrolysis of Chinese oil shale in the presence of water

A study of reaction mechanisms and chemical kinetics of pressurized pyrolysis of Chinese Liushuhe oil shale in the presence of water were conducted using an autoclave for simulating and modeling in-situ underground thermal degradation.It was found that the oil shale was first pyrolyzed to form pyrobitumen,shale oil,shale gas and residue,then the pyrobitumen was further pyrolyzed to form more shale oil,shale gas,and residue.It means that there are two consecutive and parallel reactions.With increasing temperature,the pyrobitumen yield,as intermediate,first reached a maximum,then decreased to approximately zero.The kinetics results show that both these reactions are first order.The activation energy of pyrobitumen formation from oil shale is lower than that of shale oil formation from pyrobitumen.

Reaction mechanism of self-propagating magnesiothermic reduction of ZrB_2 powders

Fine zirconium diboride （ZrB2） powders with high purity were successfully prepared by combustion synthesis through magnesiothermic reduction process in Mg-B2O3-ZrO2 system. The reaction mechanism was investigated by differential thermal analysis and quenching experiment. The results show that the whole magnesio-thermic reduction process includes three stages： first, molten B2O3 and Mg formed above the temperature of 650 ℃, and glassy B2O3 and solid ZrO2 particles were coated on the surface of the molten Mg; thus, the hollow balls can be formed when the molten Mg was exuded under capillary function. Second, ZrO2 particles reacted with molten Mg to form Zr and MgO with dissolution-precip-itation mechanism, which released a large amount of heat to induce the diffusion reaction between B203 and Mg to form B and MgO. Last, Zr reacted with B to form ZrB2 grains. The preparation of ZrB2 by self-propagating syn-thesis in Mg-B2O3-ZrO2 system is a solid-liquid-liquid reaction.

Preparation and Reaction Mechanism of Red Mud based Ceramic Simple Bricks

In order to utilize solid wastes,ceramic simple bricks with high performances were made from industrial solid wastes such as red mud,fly ash and poor clay shale as main raw materials in this paper.The phase compositions and microstructures were tested by XRD,SEM and EPMA.The experimental results show that the water absorption is 45.64%,the porosity is 58.91%,bulk density is 1.29 g·cm-3,compressive strength is 54.91 MPa,bending strength is 29.52 MPa,freeze-thaw resistance is 29.28 MPa,specific heat capacity at constant pressure is 1.31 J·g-1·K-1,thermal diffusivity is 5.89×10-3 cm2·s-1,and thermal conductivity is 1.15×10-2 W·cm-1·K-1.These effects of additives and preparation process to the properties and microstructures were discussed in detail.The reaction mechanism was also discussed.The results of the reaction mechanism show that there has wollastonite and feldspar generated during the process of firing while Ca gathered around the feldspar,and then Ca would displace K and generated cacoclasite.

Epoxidation of Styrene-Isoprene-Styrene Block Copolymer and Research on Its Reaction Mechanism

Styrene-isoprene-styrene（SIS） block copolymer was modified into epoxidized styrene-isoprene-styrene（ESIS） block copolymer with performic acid generated in situ from hydrogen peroxide and formic acid.The structure and property of ESIS were characterized by Fourier transform infrared（FT-IR） spectroscopy,gel permeation chromatography（GPC）,thermogravimetric/differential thermogravimetric（TG/DTG）,melt flow rate（MFR） and dynamic mechanical analysis（DMA）,and the reaction mechanism in the process of epoxidation was analyzed.The results showed that C=C double bonds of 1,4-structure were more active than that of 3,4-structure in polyisoprene chains.With epoxidation reaction proceeding,the whole tendency of molecular weight increased and molecular weight distribution widened,and MFR firstly increased and latterly decreased.The heat resistance of ESIS was superior to that of SIS.When SIS was changed into ESIS with 15.3% of mass fraction of epoxide groups,Tg of polyisoprene chains increased from-45.3 ℃ to 10.9 ℃.In the earlier period of epoxidation,some molecular chains ruptured and new substances with low molecular weight formed.However,in the latter period,crosslinking reaction between molecular chains which was initiated by epoxide groups or C=C double bonds occurred and crosslinked insoluble substances came into being.

Reaction Mechanism and Kinetics for HCCO Radical with NO

The mechanism and dynamical properties for the reaction of HCCO radicals with NO were investigated theoretically. The minimum energy paths(MEP) of the reaction were calculated by using the density functional theory(DFT) at the B3LYP/6-311+G ** level, and the energies along the MEP were further refined at the QCISD(T)/6-311+G ** level. It is found that the reaction mechanism of the title reaction involves three channels, producing HCNO+CO, HONC+CO and HCN+CO 2 products, respectively. Channel 1 is the most favorable path. The rate constant for channel 1 were calculated over a temperature range of 800—2500 K by using the canonical variational transition-state theory(CVT). The rate constant for the main path is negatively dependent on temperature, which is a characteristic of radical reactions with negative activation energy, and the variational effect for the rate constant calculation is small in the whole temperature range.

Theoretical Studies on the Reaction Mechanism of 1-Chloroethane with Hydroxyl Radical

The reaction mechanism of 1-chloroethane with hydroxyl radical has been investigated by using density functional theory （DFT） B3LYP/6-31G （d, p） method. All bond dissociation enthalpies were computed at the same theoretical level. It was found that hydrogen abstraction pathway is the most favorable. There are two hydrogen abstraction pathways with activation barriers of 0.630 and 4.988 kJ/mol, respectively, while chlorine abstraction pathway was not found. It was observed that activation energies have a more reasonable correlation with the reaction enthalpy changes （ΔHr） than with bond dissociation enthalpies （BDE）.