Polygonal mesopores microflower catalysts for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene to 2-nitro-4-methylsulfonylbenzoic acid in a continuous-flow microreactor

The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.

Treatment of phenol wastewater by microwave-induced CIO_2-CuO_x/Al_2O_3 catalytic oxidation process

The catalyst of CUOx/Al2O3 was prepared by the dipping-sedimentation method using y-Al2O3 as a supporter. CuO and Cu2O were loaded on the surface of Al2O3, characterized by X-ray diffraction （XRD） and X-ray photoelectron spectroscopy （XPS）. In the presence of CuOx/Al2O3, the microwave-induced chlorine dioxide （ClO2） catalytic oxidation process was conducted for the treatment of synthetic wastewater containing 100 mg/L phenol. The factors influencing phenol removal were investigated and the results showed that microwave-induced C102-CuOx/ml203 process could effectively degrade contaminants in a short reaction time with a low oxidant dosage, extensive pH range. Under a given condition （ClO2 concentration 80 mg/L, microwave power 50 W, contact time 5 latin, catalyst dosage 50 g/L, pH 9）, phenol removal percentage approached 92.24%, corresponding to 79.13% of CODcr removal. The removal of phenol by microwave-induced ClO2-CuOx/Al2O3 catalytic oxidation process was a complicated non-homogeneous solid/water reaction, which fitted pseudo-first-order by kinetics. Compared with traditional ClO2 oxidation, ClO2 catalytic oxidation and microwave-induced ClO2 oxidation, microwave-induced ClO2 catalytic oxidation system could significantly enhance the degradation efficiency. It provides an effective technology for the removal of phenol wastewater.

Catalytic Oxidation of Dimethyl Ether to Dimethoxymethane over Cs Modified H_3PW_(12)O_(40)/SiO_2 Catalysts

The attractive utilization route for one-step catalytic oxidation of dimethyl ether to dimethoxymethane was successfully carried out over the H3PW12O40（40%）/SiO2 catalyst, modified by Cs, K, Ni, and V. The Cs modification of H3PW12O40（40%）/SiO2 gave the most promising result of 20% dimethyl ether conversion and 34.8% dimethoxymethane selectivity. Dimethoxymethane could be synthe- sized via methoxy groups decomposed from dimethyl ether through the synergistic effect between the acid sites and the redox sites of Cs modified H3PW12O40（40%）/SiO2.

Catalytic Partial Oxidation of Methane over Ni/CeO_2-ZrO_2-Al_2O_3

Nickel catalysts supported on CeO2-ZrO2-CeO2,ZrO2-Al2O3 and Al2O3 were prepared and characterized by means of X-ray diffraction（XRD）,BET areas,H2 temperature-programmed reduction（H2-TPR）,and X-ray photoelectron spectroscopy（XPS）.Through the test of catalytic partial oxidation of methane（CPOM）,Ni/CeO2-ZrO2-Al2O3 displayed the highest activity,which resulted from its largest BET area and best NiO dispersion.Furthermore,Ni/CeO2-ZrO2-Al2O3 maintained a long-time stability in CPOM,which was attributed to its best coking resistance among all the prepared catalysts.

Insight into catalytic properties of Co3O4-CeO2 binary oxides for propane total oxidation

A series of Co3O4-CeO2 binary oxides with various Co/(Ce+Co)molar ratios were synthesized using a citric acid method,and their catalytic properties toward the total oxidation of propane were examined.The activities of the catalysts decrease in the order CoCeOx-70>CoCeOx-90>Co3O4>CoCeOx-50>CoCeOx-20>CeO2.CoCeOx-70(Co/(Ce+Co)=70% molar ratio)exhibits the highest catalytic activity toward the total oxidation of propane,of which the T90 is 310℃(GHSV=120000 mL h^-1 g^-1],which is 25℃ lower than that of pure Co3 O4.The enhancement of the catalytic performance of CoCeOx-70 is attributed to the strong interaction between CeO2 and Co3O4,the improvement of the low-temperature reducibility,and the increase in the number of active oxygen species.In-situ DRIFTS and reaction kinetics measurement reveal that Ce addition does not change the reaction mechanism,but promotes the adsorption and activation of propane on the catalyst surface.The addition of water vapor and CO2 in reactant gas has a negative effect on the propane conversion,and the catalyst is more sensitive to water vapor than to CO2.In addition,CoCeOx-70 exhibits excellent stability and reusability in water vapor and CO2 atmosphere.

Enhancing catalytic toluene oxidation over MnO2@Co3O4 by constructing a coupled interface

Herein,a bottom-down design is presented to successfully fabricate ZIF-derived Co3O4,grown in situ on a one-dimensional(1D)α-MnO2 material,denoted as α-MnO2@Co3O4.The synergistic effect derived from the coupled interface constructed betweenα-MnO2 and Co3O4 is responsible for the enhanced catalytic activity.The resultantα-MnO2@Co3O4 catalyst exhibits excellent catalytic activity at a T90%(temperature required to achieve a toluene conversion of 90%)of approximately 229℃,which is 47 and 28℃ lower than those of the pureα-MnO2 nanowire and Co3O4-b obtained via pyrolysis of ZIF-67,respectively.This activity is attributed to the increase in the number of surface-adsorbed oxygen species,which accelerate the oxygen mobility and enhance the redox pairs of Mn^4+/Mn^3+ and Co^2+/Co^3+.Moreover,the result of in situ diffuse reflectance infrared Fourier transform spectroscopy suggests that the gaseous oxygen could be more easily activated to adsorbed oxygen species on the surface of α-MnO2@Co3O4 than on that of α-MnO2.The catalytic reaction route of toluene oxidation over theα-MnO2@Co3O4 catalyst is as follows:toluene→benzoate species→alkanes containing oxygen functional group→CO2 and H2O.In addition,the α-MnO2@Co3O4 catalyst shows excellent stability and good water resistance for toluene oxidation.Furthermore,the preparation method can be extended to other 1D MnO2 materials.A new strategy for the development of high-performance catalysts of practical significance is provided.

Facile synthesis of 3D nanoporous Pd/Co_2O_3 composites with enhanced catalytic performance for methanol oxidation

To simultaneously reduce noble metal Pd usage and enhance electrocatalytic performance for methanol oxidation,Pd/Co2O3 composites with ultrafine three-dimensional(3D)nanoporous structures were designed and synthesized by simple one-step dealloying of a melt-spun Al-Pd-Co alloy with an alkaline solution.Their electrocatalytic activity in alkaline media was determined by a Versa-STAT MC workstation.The results indicate that the typical sizes of the ligaments and pores of the composites were approximately 8-9 nm.The Co2O3 was uniformly distributed on the Pd ligament surface.Among the as-prepared samples,the nanoporous Pd/Co2O3 composite generated from dealloying of the Al84.5Pd15Co0.5 alloy had the best electrocatalytic activity,and its activity was enhanced by approximately 230%compared with the nanoporous Pd from dealloying of Al85Pd15.The improvement of the electrocatalytic performance was mainly attributed to the electronic modification effect between Pd and Co as well as the bifunctional mechanism between Pd and Co2O3.

Synthesis of Mesoporous Cu-Mn-Al_2O_3 Materials and Their Applications to Preferential Catalytic Oxidation of CO in a Hydrogen-rich Stream

A series of mesoporous Cu-Mn-Al2O3（CMA） materials was synthesized at moderate temperature and their structures were characterized by XRD, N2 physical adsorption and TPR techniques. It was found that using metal complex ion[Cu（NH3） 4^2＋-Mn（NH3）6^2＋] as raw materials is easier to form good-structure mesoporous Cu-Mn-Al2O3 materials than using its nitrate salt [Cu（NO3）2-Mn（NO3）2]. The TPR tests results indicate that CuO and MnOx were homogeneously dispersed in the mesoporous materials. Their catalytic application to preferential catalytic oxidation of CO in a hydrogen-rich stream was studied. The activity varies in the order of CMA（1：1, molar ratio）〉 CMA（1：2）〉CMA（2：1）〉CMA（CP）〉CMA（1：0）≈CMA（0：1）. The CMA（1：0） and CMA（0：1） have lower activity compared to other samples, implying that there existed coordination effect between Cu-Mn in the samples. The selectivity varied in the order of CMA（0：1）≥CMA（1：2）〉CMA（1：1）〉CMA（2：1）〉CMA（1：0） at higher temperature （≥ 120 ℃）, indicating that increasing the Cu content enhanced the conversion of H2. The sample CMA（CP） made by coprecipitation method has a lower CO oxidation activity and selectivity than its counter-parts of mesoporous Cu-Mn-Al2O3 materials[CMA（1：2）], this attributed to the lower surface area of the former and poor interaction of CuO with MnOx.

Dielectric barrier discharge plasma synthesis of Ag/γ-Al_(2)O_(3) catalysts for catalytic oxidation of CO

In this study,Ag/γ-Al_(2)O_(3)catalysts were synthesized by an Ar dielectric barrier discharge plasma using silver nitrate as the Ag source andγ-alumina(γ-Al_(2)O_(3))as the support.It is revealed that plasma can reduce silver ions to generate crystalline silver nanoparticles(Ag NPs)of good dispersion and uniformity on the alumina surface,leading to the formation of Ag/γ-Al_(2)O_(3)catalysts in a green manner without traditional chemical reductants.Ag/γ-Al_(2)O_(3)exhibited good catalytic activity and stability in CO oxidation reactions,and the activity increased with increase in the Ag content.For catalysts with more than 2 wt%Ag,100%CO conversion can be achieved at 300°C.The catalytic activity of the Ag/γ-Al_(2)O_(3)catalysts is also closely related to the size of theγ-alumina,where Ag/nano-γ-Al_(2)O_(3)catalysts demonstrate better performance than Ag/micro-γ-Al_(2)O_(3)catalysts with the same Ag content.In addition,the catalytic properties of plasma-generated Ag/nano-γ-Al_(2)O_(3)(Ag/γ-Al_(2)O_(3)-P)catalysts were compared with those of Ag/nano-γ-Al_(2)O_(3)catalysts prepared by the traditional calcination approach(Ag/γ-Al_(2)O_(3)-C),with the plasma-generated samples demonstrating better overall performance.This simple,rapid and green plasma process is considered to be applicable for the synthesis of diverse noble metal-based catalysts.

Designing ultrastable P2/O3-type layered oxides for sodium ion batteries by regulating Na distribution and oxygen redox chemistry

P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.

Preparation,characterization and catalytic behavior of hierachically porous CuO/α-Fe_2O_3/SiO_2 composite material for CO and o-DCB oxidation

Hierachically porous （HP） CuO/α-Fe2O3/SiO2 composite material was fabricated by sol-gel method and multi-hydrothermal processes using HP-SiO2 as support.The resulting material was characterized by N2 adsorption-desorption,X-ray diffraction and scanning electron microscopy.The as-prepared CuO/Fe2O3/HP-SiO2 sample,with α-Fe2O3 and CuO nanocrystals,possessed a co-continuous skeleton,through-macroporous and mesoporous structure.Its catalytic behavior for CO and o-DCB oxidation was investigated.The result showed that CuO/Fe2O3/HP-SiO2 catalyst exhibited high catalytic activity for both CO and o-DCB oxidation,indicating its potential application in combined abatement of CO and chlorinated volatile organic compounds.

Study on the Synergistic Catalytic Oxidation of Landfill Leachate by O3 /H2O2 System

The characteristics of water quality had significant effects on the oxidative degradation of O_3/H_2O_2 system.In this study,iron supported on activated carbon catalyst was prepared firstly,and then the treatment of landfill leachate by O_3/H_2O_2/catalyst system was analyzed,especially the roles of H_2O_2 in the oxidation of landfill leachate by O_3/H_2O_2 system.The results showed that at room temperature,when the dosage of the catalyst was 1.0g,the removal rate of COD from the landfill leachate reached 79.8% after 50 ml of the landfill leachate(pH=3)was oxidized by O_3(its flow rate was 5g/h)for 50 min.If 0.3ml of H_2O_2 was added to the landfill leachate,the removal rate of COD increased from 79.8%to 88.7%.It showed that the landfill leachate with the characteristics of complex composition and difficult biodegradation could be effectively degraded by the O_3/H_2O_2 system.

Effect of Calcination Temperature on Surface Oxygen Vacancies and Catalytic Performance Towards CO Oxidation of Co3O4 Nanoparticles Supported on SiO2

Co3O4/SiO2 catalysts for CO oxidation were prepared by conventional incipient wetness impregnation followed by calcination at various temperatures. Their structures were char- acterized with X-ray diffraction （XRD）, laser Raman spectroscopy, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR） and X-ray absorption fine structure （XAFS） spectroscopy. Both XRD and Raman spectroscopy only detect the existence of Co3O4 crystallites in all catalysts. However, XPS results indicate that excess Co2＋ ions are present on the surface of Co3O4 in Co3O4（200）/Si02 as compared with bulk Co3O4. Meanwhile, TPR results suggest the presence of surface oxygen vacancies on Co3O4 in Co3O4（200）/SiO2, and XAFS results demonstrate that Co3O4 in Co3O4（200）/SIO2 contains excess Co2＋. Increasing calcination temperature results in oxidation of excess Co2＋ and the decrease of the concentration of surface oxygen vacancies, consequently the for- mation of stoichiometric Co3O4 on supported catalysts. Among all Co3O4/SiO2 catalysts, Co3O4（200）/SiO2 exhibits the best catalytic performance towards CO oxidation, demonstrating that excess Co2＋ and surface oxygen vacancies can enhance the catalytic activity of Co3O4 towards CO oxidation. These results nicely demonstrate the effect of calcination temperature on the structure and catalytic performance towards CO oxidation of silicasupported Co3O4 catalysts and highlight the important role of surface oxygen vacancies on Co3O4.

Morphology and Frictional Characteristics Under Electrical Currents of Al_2O_3/Cu Composites Prepared by Internal Oxidation

Two Al2O3/Cu composites containing 0.24 wt.% Al2O3 and 0.60 wt.% Al2O3 separately are prepared by internal oxidation. Effects of sliding speed and pressure on the frictional characteristics of the composites and copper against brass are investigated and compared. The changes in morphology of the sliding surface and subsurface are examined with scanning electron microscope （SEM） and energy dispersive X-ray spectrum （EDS）. The results show that the wear resistance of the Al2O3/Cu composites is superior to that of copper under the same conditions, Under a given electrical current, the wear rate of Al2O3/Cu composites decreases as the Al2O3-content increases, However, the wear rates of the Al2O3/Cu composites and copper increase as the sliding speed and pressure increase under dry sliding condition. The main wear mechanisms for Al2O3/Cu composites are of abrasion and adhesion; for copper, it is adhesion, although wear by oxidation and electrical erosion can also be observed as the speed and pressure rise.

Preparation of α-Bi_2O_3 from bismuth powders through low-temperature oxidation

α-Bi2O3 powders were prepared from nanometer Bi powders through low-temperature oxidation at less than 873.15 K. XRD, SEM, TEM and HRTEM were used to characterize the structure and morphology of Bi powders and Bi2O3 particles. Kinetic studies on the bismuth oxidation at low-temperatures were carried out by TGA method. The results show that bismuth beads should be reunited and oxidized to become irregular Bi2O3 powders. The bismuth oxidation follows shrinking core model, and its controlling mechanism varies at different reaction time. Within 0-10 min, the kinetics is controlled by chemical reaction, after that it is controlled by O2 diffusion in the solid α-Bi2O3 layer. The apparent activation energy is determined as 55.19 kJ/mol in liquid-phase oxidation.

Effect of La_2O_3/Ce O_2 particle size on high-temperature oxidation resistance of electrodeposited Ni-La_2O_3/Ce O_2 composites

Ni-La2O3/CeO2 composite films were prepared by electrodeposition from a nickel sulfate bath containing certain content of micrometer and nanometer La2O3/CeO2 particles. The effect of La2O3 or CeO2 particle size on the oxidation resistance of the electrodeposited Ni-La2O3/CeO2 composites in air at 1000 °C was studied. The results indicate that, compared with the electrodeposited Ni-film, Ni-La2O3/CeO2 composites exhibit a superior oxidation resistance due to the codeposited La2O3 or CeO2 particles blocking the outward diffusion of nickel. Moreover, compared with nanoparticles, La2O3 or CeO2 microparticles have stronger effect because La2O3 or CeO2 microparticles also act as a diffusion barrier layer at the onset of oxidation.

Impedance spectroscopy study of high-temperature oxidation of Gd_2O_3-Yb_2O_3 codoped zirconia thermal barrier coatings

3Gd2O3-3Yb2O3-4Y2O3 （mole fraction, %） co-doped ZrO2 （GY-YSZ） thermal barrier coatings （TBCs） were produced by electron beam physical vapor deposition （EB-PVD）. The oxidation behavior of GY-YSZ at 1 050 ℃ was investigated using impedance spectroscopy （IS） combined with scanning electron microscopy （SEM）, Raman spectroscopy and X-ray diffractometry （XRD）. Various electrical responses observed in the impedance spectra corresponding to GY-YSZ grains and grain boundaries were explained using circuit modeling. The change in the conduction mechanism of GY-YSZ was found to be related to the O^2- vacancy and lattice distortion due to the stabilizer diffusion during the oxidation. The results also suggested that the specific oxidation information about the GY-YSZ grains and grain boundaries should be acquired at a moderate measurement temperature, which was related to the resistance value in the impedance spectra. The resistance values of the GY-YSZ grains and grain boundaries should be measured at 200 ℃ and 300 ℃, respectively.

Preparation of Al_2O_3/Au nano-laminated composite coatings and their oxidation resistance on stainless steel

Al2O3/Au nano-laminated composite coatings were prepared by means of magnetron sputtering. The coating was compact and comprised of nano-laminated Al2O3 and Au layers. High temperature cyclic oxidation test was employed to investigate the oxidation resistance of the composite coatings. The results revealed that the applied Al2O3/Au nano-laminated composite coatings improved the oxidation and spallation resistance of the stainless steel substrate significantly. The mechanism accounting for oxidation resistance was related with the suppression of inward oxygen diffusion and selective oxidation of Cr in the substrate. The mechanism accounting for spallation resistance was attributed to the relaxation of thermal stress by the nano-laminated structure.

Prospect of vapor phase catalytic H2O2 production by oxidation of water

Vapor phase catalytic hydrogen peroxide production by oxidation of water is possible by coupling the reaction with oxidation of an organic sacrificial reductant. It is potentially a safer process than direct synthesis from H2 and O2. Based on mechanistic information available mostly for liquid phase catalytic processes, feasible reaction mechanisms for such coupled reactions are proposed based on which desirable catalyst properties are identified. It is found that the surface-adsorbed oxygen bond is an important parameter for identifying desirable catalysts. Thermodynamics can be used to identify the types of organic oxidation reactions that can couple with water oxidation such that H2O2 formation becomes thermodynamically favorable. Reactions such as epoxidation of alkenes and selective oxidation of alkanes to alcohols cannot provide sufficient thermodynamic driving force, whereas oxidation of alcohols to aldehydes and to acids can. Finally, further research is suggested to identify catalytic properties important for H2O2 decomposition and for coupling selective oxidation of organic compounds to oxidation of H2O in order to facilitate development of H2O2 production coupled with selective organic oxidation.

Effect of Cu Loading to Catalytic Selective CO Oxidation of CuO/CeO₂–Co₃O₄

This work studied CuO/CeO2-Co3O4 with wt% Ce:Co ratio 95:5 for selective CO oxidation with effect of? wt% Cu loading. The catalysts were prepared by co-precipitation. Characterizations of catalysts were carried out by XRD and BET techniques. The results showed a good dispersion of CuO for 5 wt% Cu loading catalysts and showed high specific surface area of catalyst. For selective CO oxidation, both 5CuO and 30CuO catalysts could remove completely CO in the presence of excess hydrogen at 423 K and 20CuO could eliminate CO completely at 443 K. Moreover, considering the selectivity to CO oxidation, the 5CuO catalyst has shown the highest selectivity of 85% while the 30CuO catalyst obtains the selectivity of 65% at the reaction temperature of 423 K.