Progress in Processes and Catalysts for Dehydrogenation of Cyclohexanol to Cyclohexanone

The dehydrogenation of cyclohexanol to cyclohexanone is a crucial industrial process in the production of caprolactam and adipic acid, both of which serve as important precursors in nylon textiles. This endothermic reaction is constrained by thermodynamic equilibrium and involves a complex reaction network, leading to a heightened focus on catalysts and process design. Copper-based catalysts have been extensively studied and exhibit exceptional low-temperature catalytic performance in cyclohexanol dehydrogenation, with some being commercially used in the industry. This paper specifically concentrates on research advancement concerning active species, reaction mechanisms, factors influencing product selectivity, and the deactivation behaviors of copper-based catalysts. Moreover, a brief introduction to the new processes that break thermodynamic equilibrium via reaction coupling and their corresponding catalysts is summarized here as well. These reviews may off er guidance and potential avenues for further investigations into catalysts and processes for cyclohexanol dehydrogenation.

Effects of reaction parameters on preparation of Cu nanoparticles via aqueous solution reduction method with NaBH_4

The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.

Ligand Size Effect on PdLn Oxidative Addition with Aryl Bromide： A DFT Study

The process and mechanism of the ligand volume controlled Pd（PR3）2 （PR3=PH3, PMe3, and PtBu3） oxidative addition with aryl bromide were investigated, using density functional theory method with the conductor-like screening model. Association pathway and dissocia-tion pathway were investigated by the comparison of several energies. The cleavage energy of Pd（PR3）2 complex was calculated, as well as the oxidative addition reaction barrier energy of Pd（PR3）n （n=1,2） with aryl bromide in N,N-dimethylformamide solvent. This study proved that the ligands volume possessed a great impact on the mechanism of oxidative addition： less bulky ligand palladium associated with aryl bromide via two donor ligands,but larger bulky ligand palladium coordinated via monoligand.

Preparation and sintering properties of zirconia-mullite-corundum composites using fly ash and zircon

Zirconia-mullite-corundum composites were successfully prepared from fly ash,zircon and alumina powder by a reaction sintering process.The phase and microstructure evolutions of the composite synthesized at desired temperatures of 1 400,1 500 and 1 600°C for 4 h were characterized by X-ray diffractometry and scanning electronic microscopy,respectively.The influences of sintering temperature on shrinkage ratio,apparent porosity and bulk density of the synthesized composite were investigated.The formation process of the composites was discussed in detail.The results show that the zirconia-mullite-corundum composites with good sintering properties can be prepared at 1 600°C for 4 h.Zirconia particles can be homogeneously distributed in mullite matrix,and the zirconia particles are around 5μm.The formation process of zirconia-mullite-corundum composites consists of decomposition of zircon and mullitization process.

Progress and challenges of carbon-fueled solid oxide fuel cells anode

Carbon-fueled solid oxide fuel cells(CF-SOFCs)can electrochemically convert the chemical energy in carbon into electricity,which demonstrate both superior electrical efficiency and fuel utilisation compared to all other types of fuel cells.However,using solid carbon as the fuel of SOFCs also faces some challenges,the fluid mobility and reactive activity of carbon-based fuels are much lower than those of gaseous fuels.Therefore,the anode reaction kinetics plays a crucial role in determining the electrochemical performance of CF-SOFCs.Herein,the progress of various anodes in CF-SOFCs is reviewed from the perspective of material compositions,electrochemical performance and microstructures.Challenges faced in developing high performance anodes for CF-SOFCs are also discussed.

Reaction Process of Chromium Slag Reduced by Industrial Waste in Solid Phase

M, a particular industrial waste, was selected to detoxify chromium slag at a high temperature. The carbon remaining in M reduced Cr （ Ⅳ ） of Na2 CrO4 borne in the chromium slag to Cr （ Ⅲ ） in the solid phase reaction, and its thermodynamics and kinetics were studied. The reduction process of Na2CrO4 by carbon produced CO, whiCh＇was endothermic. Under the experimental condition, the apparent activation energy was 4. 41 kJ·mol^-1 , the＇apparent order of reaction for Na2 CrO4 was equal to one, and the partial pressure of CO was only 0.22 Pa at 1 330℃.

Self-assembled synthesis of oxygen-doped g-C3N4 nanotubes in enhancement of visible-light photocatalytic hydrogen

Currently,photocatalytic water splitting is regarded as promising technology in renewable energy generation.However,the conversion efficiency suffers great restriction due to the rapid recombination of charge carriers.Rational designed the structure and doping elements become important alternative routes to improve the performance of photocatalyst.In this work,we rational designed oxygen-doped graphitic carbon nitride(OCN)nanotubes derived from supermolecular intermediates for photocata lytic water splitting.The as prepared OCN nanotubes exhibit an outstanding hydrogen evolution rate of 73.84μmol h^(-1),outperforming the most of reported one dimensional(1D)g-C_(3)N_(4) previously.Due to the rational oxygen doping,the band structure of g-C_(3)N_(4) is meliorated,which can narrow the band gap and reduce the recombination rate of photogene rated carriers.Furthermore,the hollow nanotube structure of OCN also provide multiple diffuse reflection during photocata lytic reaction,which can significantly promote the utilization capacity of visible light and enhance the photocatalytic water splitting performance.It is believed that our work not only rationally controls the nanostructure,but also introduces useful heteroatom into the matrix of photocatalyst,which provides an effective way to design high-efficiency g-C_(3)N_(4) photocatalyst.

IN SITU PROCESSING OF Al_(2)O_(3) WHISKERS REINFORCED Ti-Al INTERMETALLIC COMPOSITES

In situ Al2O3 whiskers reinforced Ti-Al intermetallic composites were fabricated at ~1200℃ by reaction sintering of cold-consolidated fillets consisting mainly of Ti, Al, and different additives. The phases and microstructures of the sintered composites were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS). The process of synthesis was investigated using differential thermal analysis (DTA). The effects of processing parameters and additives on the microstructures of the composites and the development of whisker were examined. It is found that the morphology of the whisker is strongly influenced by the additives, the exothermal reaction process, and the processing parameters.

Reaction mechanism of roasting Zn_2SiO_4 using NaOH

The reaction kinetics of roasting zinc silicate using NaOH was investigated.The orthogonal test was employed to optimize the reaction conditions and the optimized reaction conditions were as follows:molar ratio of NaOH to Zn2SiO4 of 16:1,reaction temperature of 550°C,and reaction time of 2.5 h.In order to ascertain the phases transformation and reaction processes of zinc oxide and silica,the XRD phase analysis was used to analyze the phases of these specimens roasted at different temperatures.The final phases of the specimen roasted at 600°C were Na2ZnO2,Na4SiO4,Na2ZnSiO4 and NaOH.The reaction kinetic equation of roasting was determined by the shrinking unreacted core model.Aiming to investigate the reaction mechanism,two control models of reaction rate were applied:chemical reaction at the particle surface and diffusion through the product layer.The results indicated that the diffusion through the product layer model described the reaction process well.The apparent activation energy of the roasting was 19.77 kJ/mol.

Advanced oxidation technology for H_2S odor gas using non-thermal plasma

Non-thermal plasma technology is a new type of odor treatment processing.We deal with H2Sfrom waste gas emission using non-thermal plasma generated by dielectric barrier discharge.On the basis of two criteria,removal efficiency and absolute removal amount,we deeply investigate the changes in electrical parameters and process parameters,and the reaction process of the influence of ozone on H2S gas removal.The experimental results show that H2S removal efficiency is proportional to the voltage,frequency,power,residence time and energy efficiency,while it is inversely proportional to the initial concentration of H2S gas,and ozone concentration.This study lays the foundations of non-thermal plasma technology for further commercial application.

DBU-based CO2 absorption-mineralization system: Reaction process,feasibility and process intensification

Amine-based carbon dioxide(CO2)capture is still limited by high desorption energy consumption.Fixing CO2 into carbonate is a safer and more permanent method.In this work,calcium oxide(CaO)is introduced to perform chemical desorption instead of thermal desorption on 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU)aqueous solution after CO2 absorption.The X-ray diffraction(XRD)patterns of solid products show the formation of calcite calcium carbonate(CaCO3),which prove the feasibility of this method.The effects of reaction temperature,reaction time and Ca2+/CO32-molar ratios on the related reactions in CO2 absorption-mineralization process and CaCO3 precipitation are discussed,and purer CaCO3 is obtained by ultrasonic treatment.The CaCO3 content can be increased to 95.8%and the CO2 desorption ratio can achieve 80%by 30 min ultrasonic dispersion treatment under the conditions(40℃,180 min,Ca2+/CO32-molar ratio=1.0).After five cycles,DBU aqueous solution shows stable CO2 absorption and mineralization ability.Fourier transform infrared spectroscopy(FT-IR)spectra of the reaction process also indicate the regeneration of the solvent.Compared with thermal desorption,this process is exothermic,almost without no additional heat.

Preparation of β-Sialon/ZrN bonded corundum composites from zircon by nitridation reaction sintering process

β-Sialon/ZrN bonded corundum composites were synthesized using fused white corundum,alumina micro powder,zircon and carbon black by nitridation reaction sintering process. Phase composition and microstructure of the synthesized composites were investigated by X-ray powder diffraction and scanning electronic microscope,and the formation process of the composites was discussed. The results show that the composites with different compositions can be obtained by controlling the heating temperature and contents of zircon and carbon black. The proper temperature to synthesize the composites is 1773 K.

Preparation of Cu nanoparticles with NaBH_4 by aqueous reduction method

Cu nanoparticles were prepared by reducing Cu2＋ ions with NaBH4 in alkaline solution. The effects of NaBH4 concentration and dripping rate on the formation of Cu nanoparticles were studied. The optimum conditions are found to be 0.2 mol/L Cu2＋, solution with pH=12, temperature of 313 K and 1% gelatin as dispersant, to which 0.4 mol/L NaBH4 is added at a dripping rate of 50 mL/min. NH3-H2O is found to be the optimal complexant to form the Cu precursor. A series experiments were conducted to study the reaction process at different time points.

Reaction dynamics in the combustion synthesis system of Al-CrO_3-Al_2O_3-NaF-N_2-O_2

A new material with heat-resistant and adiabatic characteristics and high strength was prepared using the combustion synthesis method by mixed powders of CrO3, Al, Al2O3, and NaF in atmospheric gas. The reaction dynamic process of the Al-CrO3-NaF-Al2O3-N2-O2 new material system by the combustion synthesis method was discussed based on the observation results by SEM, EDS, and XRD in combination with the combustion front quenching method （CFQM） and the relation curves between reaction free enthalpies and the corresponding temperatures. The combustion synthesis mechanism and the formation reasons of the phase in the combustion product were analyzed.

Fabrication of an r-Al_2Ti intermetallic matrix composite reinforced with α-Al_2O_3 ceramic by discontinuous mechanical milling for thermite reaction

In this study, a powder mixture with an Al/TiO2 molar ratio of 10/3 was used to form an r-Al2Ti intermetallic matrix composite （IMC） reinforced with α-Al2O3 ceramic by a novel milling technique, called discontinuous mechanical milling （DMM） instead of milling and ignition of the produced thermite. The results of energy dispersive X-ray spectroscopy （EDX） and X-ray diffraction （XRD） of samples with varying milling time indicate that this fabrication process requires considerable mechanical energy. It is shown that Al2Ti-α-Al2O3 IMC with small grain size was produced by DMM after 15 h of ball milling. Peaks for γ-TLA1 as well as Al2Ti and Al2O3 are observed in XRD patterns after DMM followed by heat treatment. The microhardness of the DMM-treated composite produced after heat treatment was higher than Hv 700.

Piezoelectric and dielectric properties of Cr-doped PSN-PZN-PZT qua-ternary piezoelectric ceramics

PSN-PZN-PZT + x wt. %Cr2O3, X = 0.0-0-9, were prepared by conventional mixed oxide techniques at sintering temperatures of 1220 degrees C-1300 degrees C for 2 h. The effect of sintering temperature on the microstructure and the piezoelectric properties was investigated by XRD, SEM, and other conventional measurement. The result indicated that with temperature increasing, the valence of Cr ion from Cr5+ or Cr6+ changes into C3+, and the piezoelectric properties turn hard. With increasing Cr2O3 content, the amount of rhombohedral phases increases and the morphotropic boundary phase is correspondingly shifts to rhombohedral phase. A uniform microstructure and excellent comprehensive properties were obtained at 1240 degrees C as the amount of Cr2O3 is 0.5 wt.%.

Facile construction of Bi2Mo3O12@Bi2O2CO3 heterojunctions for enhanced photocatalytic efficiency toward NO removal and study of the conversion process

Charge separation and transformation are some of the key requirements for high-efficiency photocatalysis. The photocatalytic reaction mechanism provides a guideline for the development and commercialization of high-efficiency photocatalysts. In this study, we designed and favorably synthesized BMO@BOC heterojunctions via a facile solvothermal route and applied the heat treatment method for application in high-efficiency photocatalytic NO removal. More importantly, both continuous stream and intermittent stream methods with in situ diffuse reflectance infrared Fourier transform spectroscopy were applied to intuitively and dynamically investigate the adsorption process and oxidation process of NO removal over the photocatalyst surface. The intermediate products(NO-, NO2-, and NO2) were explicitly detected in both the adsorption process and oxidation process, whilst the final product(NO3-) appeared only in the oxidation process, owing to the separation, migration, and conversion of photoinduced electron-hole pairs.

The Process of TiB_2-Cu Composite Phase and Structure Formation during Combustion Synthesis

The reaction process of combustion synthesis for TiB2 -Cu was investigated in detail using combustion-wave arresting experiment, X-ray diffraction （ XRD ） analysis, SEM analysis and differential thermal analysis （ DTA ）. The XRD analysis results for the different parts of the quenched specimen show that TiCux intermetallic phase firstly forms with the propagation of combustion wave, and then Ti1.87 B50 and Ti3B4 metastable phases come forth due to the diffusion of B atoms and finally the stable TiB2 phase forms because of the continuous diffusion of B atoms. The formation of TiB2 phase is uot completed by one step, but undergoes several transient processes. The process of reaction synthesis for Ti-B-Cu ternary system can be divided into three main stages： melting of Cu and Ti , and the formation of Cu- Ti melt and few TiCux , TiBx intermetallic phases ; large numbers of TiCux intermetallic phases formation and some fine TiB2 particles precipitation ; and the TiB2 particles coarsening and the stable TiB2 and Cu two phases formation in the final product.

Ionic Charge State Distribution of Au Plasma for 7-Ion System

The present work extends the previous work^[2] on 5-ion system to consider 7-ion system （i.e., Au^47＋ -Au^53＋）. It is found that more highly charged ions, e.g., Au^53＋, Au^54＋ etc., could be able to be neglected, however, less highly charged ions, e.g., Au^47＋, Au^46＋ etc., are rather important. Therefore, a new idea to consider 8-ion system, i.e., Au^46＋ - Au^53＋, is under way. As a supplement, we discuss the simultaneous reaction, which would be important in this sort of works.

Experimental study and theoretical analysis on the effect of electric field on gas explosion and its propagation

The effect of the electric field with different intensity on explosion wave pressure and flame propagation velocity of gas explosion was experimentally studied, and the effect of electric field on gas explosion and its propagation was theoretically analyzed from heat transportation, mass transportation, and reaction process of gas explosion. The results show that the electric field can affect gas explosion by enhancing explosion intensity and explosion pressure, thus increasing flame velocity. The electric field can offer energy to the gas explosion reaction; the effect of the electric field on gas explosion increases with the increase of electric field intensity. The electric field can increase mass transfer action, heat transfer action, convection effects, diffusion coefficient, and the reaction system entropy, which make the turbulence of gas explosion in electric field increase; therefore, the electric field can improve flame combustion velocity and flame propagation velocity, release more energy, increase shock wave energy, and then promote the gas explosion and its propagation.