A review of the direct oxidation of methane to methanol

This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts.

Electron transfer to direct oxidation of aqueous organics by perovskites

The residual of oxidant chemicals in advanced oxidation processes(AOPs)resulted in both economic cost and secondary pollution.Herein,we report a direct oxidation of phenolic pollutants induced by Ca-Mn-O perovskites without using an oxidant.Governed by one-electron transfer process(ETP)from the phenolics to the Ca-Mn-O perovskites,this direct oxidation proceeds in fast reaction kinetics with activation energy of 51.4 kJ/mol,which was comparable with those AOPs-based catalytic systems.Additionally,mineralization and polymerization reactions occurred on the Ca-Mn-O surface and ensured the complete removal of phenolics.The high spin state Mn(III)within Ca-Mn-O structure was the dominant active site for this ETP.The elongated axial Mn(III)–O bonds within the[MnO_(6)]octahedron facilitated the acceptance of the electrons from the phenolics and thus promoted the initiation of the direct oxidation process.Mn(III)in the high spin state can also activate dissolved O_(2)to produce singlet oxygen(^(1)O_(2))for a fast removal of phenolics.The mixed Mn(III)/Mn(IV)within Ca-Mn-O accelerated the ETP by enhancing the electrical conductivity.This efficient Ca-Mn-O-induced ETP for removal of organic contaminants casts off the dependence on external chemical and energy inputs and provides a sustainable approach for transforming the toxic organic pollutants into value-added polymers.

Formation Mechanism of Nanoparticles in Fe-Cr-Al ODS Alloy Fabricated by Direct Oxidation Method

This study presents the fabrication of 14CrFe-Cr-Al oxide dispersion strengthened(ODS)alloy by a direct oxidation process.In order to explain how oxide nanoparticles are formed in the consolidation process,the powders after oxidation are subjected to vacuum thermal treatment at high temperatures.Differential scanning calorimeter,X-ray photoelectron spectroscopy,scanning electron microscopy and transmission electron microscopy techniques are used to detect the generation,evolution of oxides on both the surface and interior of the powder,as well as the type of oxide nanoparticles in the fabricated ODS alloy.It is found that an iron oxide layer is formed on the surface of the powder during low temperature oxidation.And the iron oxide layer would be decomposed after thermal treatment at high temperature.In the consolidation process,the oxygen required by the reaction of alumina and yttrium oxide to produce nano scale Y-Al-O particles mainly derives from the decomposition of iron oxide layer at elevated temperature and the inward diffusion of oxygen.Using the direct oxidation process,YAlO_(3) nanoparticles are dispersed in the grains and at the grain boundaries of Fe-Cr-Al ODS alloy.

Fabrication of Ceramic Composites by Directed Metal Oxidation

To explain the growth mechanism of Al 2O 3/Al Lanxide composites,the dynamics of the directed oxidation of Al-Mg-Si alloys are analyzed.The experimental methods to produce Lanxide composites by directed oxidation of metal melts at high temperatures are presented.The effect of the processing factors on the microstructures and properties of Al 2O 3/Al composites and enforced Al 2O 3/Al composites is also analyzed.Compared with sintering ceramic composites,the advantages of Lanxide process and Lanxide materials are as following:it is a near net shaped process;the process is very simple;the microstructures and properties of Lanxide materials can be adjusted;and this process can be used to infiltrate ceramic fiber or particle preforms.

Preparation of SiC_p/Al_2O_3-Al Composites by Directed Metal Oxidation

SiCp/Al2O3-Al composites were synthesized by means of direct metal oxidation method. The composition and microstructures of the composites were investigated using X-ray diffraction （XRD）, scanning electron microscopy （SEM） and metallurgical microscope. The effects of technical parameters on the properties of the product were analyzed. The results indicate that the composite possesses a dense microstructure, composed of three interpenetrated phases. Of them, SiO2 layer prohibits the powdering of the composites; Mg promotes the wetting and infiltration of the system and Si restricts the interfacial reaction while improving the wetting ability between reinforcement and matrix.

Ultrasonic-assisted Oxidation Leaching of Nickel Sulfide Concentrate

The feasibility of oxidation leaching process of nickel from nickel sulfide ore and the form of different components in the lixivium has been studied at first. The method of leaching nickel sulfide concentration directly by oxidants with existence of ultrasonic has been advanced. The process of leaching nickel from nickel sulfide concentration by using the system of persulfate and silver has been determined. The influence of different factors on the leaching rates of nickel,such as with and without ultrasonic,the concentration of Na2S2O8,liquid-solid ratio and the concentration of AgNO3 have been explored. The results show that:(1) in the oxidative leaching system,nickel can be leached completely as Ni2+ or NiSO4(aq.) from nickel sulfide concentration in theory;(2) the nicopyrite can not exist steadily in the persulfate acid leaching system,but Ni2+can. Meanwhile,sulfur may be existed steadily in the leaching process;(3) nicopyrite with much lower electrostatic potential may be leached earlier than chalcopyrite and sideropyrite;and(4) the overall reaction rate of the leaching process can be enhanced with ultrasonic radiation,but it does not change the mechanism of leaching. The more oxidant concentration or higher liquid-solid ratio is,the higher leaching percentage of nickel. The leaching percentage of nickel can be increased significantly by adding a small amount of AgNO3 during the leaching processes. Under the same conditions,the higher concentration of AgNO3 is,the higher leaching yields of nickel will be obtained.

Different Performances of H_2O_2 to Oxidise Aldicarb and Hexazinone in the Advanced Oxidation Process of Ozone/Hydrogen Peroxide

The degradations of hexazinone and aldicarb by direct ozonation combined an advanced oxidation process( AOP) of O3/H2O2 were investigated in this study focusing on the oxidation mechanism by identifying the hydrogen peroxide consumption during the oxidation process of the two chemicals. The results showed that H2O2 could enhance the removal rate of the triazine herbicide hexazinone,and it was consumed along with the variation of removal rate in the light of different pH levels. The addition of H2O2 contributed little to the removal of the thiocarbamate herbicide aldicarb and H2O2 content kept constantly throughout the degradation process. Tert-butyl alcohol( TBA) effectively scavenged the ·OH radical for hexazinone,but had no effect on the removal rate of aldicarb. Aldicarb removal was mainly attributed to direct ozonation molecule in both O3( 97.00%) and O3/H2O2( 96.76%)systems. Moreover,sole O3 could hardly oxidize hexazinone whereas·OH radicals contribute respective 74.70% and 97.50% of removal in O3 system and O3/H2O2 AOP. All of these findings suggest that the mechanism of ·OH radical generation and the chain reaction in O3/H2O2 AOP should be further discussed.

La_(0.75)Sr_(0.25)Cr_(0.5)Mn_(0.5)O_(3)-δ−Ce_(0.8)Gd_(0.2)O_(1.9) composite electrodes as anodes in LaGaO_(3)-based direct carbon solid oxide fuel cells

Direct carbon solid oxide fuel cells(DC-SOFCs)are promising,green,and efficient power-generating devices that are fueled by solid carbons and comprise all-solid-state structures.Developing suitable anode materials for DC-SOFCs is a substantial scientific challenge.Herein we investigated the use of La_(0.75)Sr_(0.25)Cr_(0.5)Mn_(0.5)O_(3)-δ−Ce_(0.8)Gd_(0.2)O_(1.9)(LSCM−GDC)composite electrodes as anodes for La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(3)-δelectrolyte-based DC-SOFCs,with Camellia oleifera shell char as the carbon fuel.The LSCM−GDC-anode DC-SOFC delivered a maximum power density of 221 mW/cm^(2) at 800℃ and it significantly improved to 425 mW/cm^(2) after Ni nanoparticles were introduced into the LSCM−GDC anode through wet impregnation.The microstructures of the prepared anodes were characterized,and the stability of the anode in a DC-SOFC and the influence of catalytic activity on open circuit voltage were studied.The above results indicate that LSCM–GDC anode is promising to be applied in DC-SOFCs.

Direct decomposition of nitric oxide in low temperature over iron-based perovskite-type catalyst modified by Ru

Iron-based perovskite-type compounds modified by Ru were prepared through sol-gel process to study its catalytic activity of NOx direct decomposition at low temperature and evaluate the conversion of NO under the experimental conditions. The catalytic activity of La 0.9Ce 0.1Fe 0.8-nCo 0.2RunO3 （n=0.01,0.03,0.05,0.07,0.09）series for the NO, NO-CO two components, CO-HC-NO three components were also analyzed. The catalytic investigation evidenced that the presence of Ru is necessary for making highly activity in decomposition of nitric oxide even at low temperature（400 ℃）and La 0.9Ce 0.9Fe 0.75Co 0.2Ru 0.05O3 （n=0.05） has better activity in all the samples, the conversion of it is 58.5%. With the reducing gas（CO,C3H6）added into the gas, the catalyst displayed very high activity in decomposition of NO and the conversion of it is 80% and 92.5% separately.

Two-dimensional PtRu Nanoclusters Carbon Based Electrocatalysts for Methanol Oxidation

A novel method to prepare an electrocatalyst with a new structure and high catalytic performance was reported. Two-dimensional（2 D） PtRu nanoclusters have been successfully deposited on graphene oxide and carbon black supports. Compared with the commercial 3 D E-TEK PtRu samples, the prepared 2 D PtRu composites have larger electrochemically active surface area and display much higher catalytic activity toward methanol oxidation reaction. The preparation method mainly includes the following procedures： oxidation of carbon matrix, Pb^（2＋） adsorption on the surface of carbon support, Pb^（2＋） electrochemical reduction and galvanic displacement of Pb^0 by Pt^（2＋） and Ru^（3＋）. The method developed in this study could be viable for solving the problem of low electrocatalytic activity in direct methanol fuel cell anodes.

Pd catalysts supported on rGO-TiO_2 composites for direct synthesis of H_2O_2: Modification of Pd^(2+)/Pd^0 ratio and hydrophilic property

The use of nanostructured composites as catalyst supports is a promising route to prepare catalysts with high selectivity and productivity. In this work, reduced graphene oxide-TiO_2(rGP-x) composites with a variation of reduced graphene oxide(rGO) content were synthesized by hydrothermal method. Pd/rGP-x catalysts were prepared in incipient-wetness impregnation method for the direct synthesis of H_2O_2 from H2 and O_2. The morphology and electronic properties of catalysts were investigated by XPS, TEM, and Raman spectroscopy.The ratio of Pd^(2+)/Pd^0 and the hydrophobicity of the catalysts were increased with the rising content of rGO. As the amount of rGO in the catalysts varied in the range of 0.025 wt%–2 wt%, the selectivity of H_2O_2 exhibited a tendency of increasing firstly and then decreasing from 0.1 wt% to 2 wt%. It indicates that good catalytic performance for H_2O_2 synthesis can be achieved only when appropriate amount of rGO is introduced. The H_2O_2 selectivity and productivity of Pd/r GP-0.025 both improved remarkably compared with Pd/P25. This enhancement originated from the combined effects of the proper ratio of Pd^(2+)/Pd^0 and hydrophobicity of the catalyst.

A review:Advances in microbial remediation of trichloroethylene (TCE)

Research works in the recent past have revealed three major biodegradation processes leading to the degradation of trichloroethylene. Reductive dechlorination is an anaerobic process in which chlorinated ethenes are used as electron acceptors. On the other hand, cometabolism requires oxygen for enzymatic degradation of chlorinated ethenes, which however yields no benefit for the bacteria involved. The third process is direct oxidation under aerobic conditions whereby chlorinated ethenes are directly used as electron donors by microorganisms. This review presented the current research trend in understanding biodegradation mechanisms with regard to their field applications. All the techniques used are evaluated, with the focus being on various factors that influence the process and the outcome.

Ce-Fe-O mixed oxide as oxygen carrier for the direct partial oxidation of methane to syngas

The Ce-Fe-O mixed oxide with a ratio of Ce/Fe=7:3, which was prepared by coprecipitation method and employed as oxygen carrier, for direct partial oxidation of methane to syngas in the absence of gaseous oxygen was explored. The mixed oxide was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), and the catalytic performances were studied in a fixed-bed quartz reactor and a thermogravimetric reactor, respectively. Approximately 99.4% H2 se...

A method for recovery of iron,titanium,and vanadium from vanadium-bearing titanomagnetite

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures： low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70 wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

Investigation of Nickel Oxide Used for Alloying in BOF Steelmaking

Direct alloying of nickel oxide in a hot simulator of LD converter was investigated in laboratory.Reduction rate of nickel oxide in steelmaking process was analyzed with the test results. Under the condition oflower slag viscosity, the reduction rate of NiO increases and the [Ni] yield rises. When the slag viscosity is higher, a lot of metal particles with higher Ni content are contained in the slag so as to decrease the [Ni] yield.

Modulating reaction pathways of formic acid oxidation for optimized electrocatalytic performance of PtAu/CoNC

Formic acid oxidation(FAO)is a typical anode reaction in fuel cells that can be facilitated by modulating its direct and indirect reaction pathways.Herein,PtAu bimetallic nanoparticles loaded onto Co and N co-doping carbon nanoframes(CoNC NFs)were designed to improve the selectivity of the direct reaction pathway for efficient FAO.Based on these subtle nanomaterials,the influences of elemental composition and carbon-support materials on the two pathways of FAO were investigated in detail.The results of fuel cell tests verified that the appropriate amount of Au in PtAu/CoNC can promote a direct reaction pathway for FAO,which is crucial for enhancing the oxidation efficiency of formic acid.In particular,the obtained PtAu/CoNC with an optimal Pt/Au atomic ratio of 1:1(PtAu/CoNC-3)manifests the best catalytic performance among the analogous obtained Pt-based electrocatalysts.The FAO mass activity of the PtAu/CoNC-3 sample reached 0.88 A·mg_(Pt)^(-1),which is 26.0 times higher than that of Pt/C.The results of first-principles calculation and CO stripping jointly demonstrate that the CO adsorption of PtAu/CoNC is considerably lower than that of Pt/CoNC and PtAu/C,which indicates that the synergistic effect of Pt,Au,and CoNC NFs is critical for the resistance of Pt to CO poisoning.This work is of great significance for a deeper understanding of the oxidation mechanism of formic acid and provides a feasible and promising strategy for enhancing the catalytic performance of the catalyst by improving the direct reaction pathway for FAO.

Microstructure and High-Temperature Oxidation Behavior of Dy-Doped Nb–Si-Based Alloys

Microstructures and oxidation behaviors of four Dy-doped Nb-Si-based alloys at 1250 ℃ were investigated. The nominal compositions of the four alloys are Nb-15Si-24Ti-4Cr-2Al-2Hf-xDy （at.%）, where x = 0, 0.05, 0.10 and 0.15, respectively. Results showed that the four alloys all consisted of Nbss, αNbsSi3 and γNbsSi3, and the addition of Dy produced no obvious effect on the phase constitution and the microstructures of Nb-Si-based alloys. After oxidation at 1250 ℃ for 58 h, it was found that the addition of Dy accelerated the oxidation rate of Nb-Si-based alloys and caused a larger weight gain, accompanied by the formation of a more porous and less protective oxide scale. The oxides of Nb2O5, Ti2Nb10O29, TiNb2O7, Ti0.4Cr0.3Nb0.302 and glassy SiO2 were formed on Dy-doped Nb-Si-based alloys. The high- temperature oxidation mechanism of Dy-doped Nb-Si-based alloys was discussed.

Recent progress in Ru(Ⅱ)-catalyzed C-H activations with oxidizing directing groups

In this review, we highlight the recent development in Ru（II）-catalyzed C-H activations under redox neutral conditions. After a brief introduction of the C-H activations with oxidizing direct group by different transition metal catalysts, the examples with Ru（ll） catalyst were classified and introduced according to different internal oxidants used in the system. The features of each methodology will be highlighted and the plausible reaction mechanism will be presented if available.

Rare earth metal oxides as BH_4^--tolerance cathode electrocatalysts for direct borohydride fuel cells

Rare earth metal oxides（REMO） as cathode electrocatalysts in direct borohydride fuel cell（DBFC） were investigated.The REMO electrocatalysts tested showed favorable activity to the oxygen electro-reduction reaction and strong tolerance to the attack of BH 4-in alkaline electrolytes.The simple membraneless DBFCs using REMO as cathode electrocatalyst and using hydrogen storage alloy as anodic electrocatalyst exhibited an open circuit of about 1 V and peak power of above 60 mW/cm 2.The DBFC using Sm 2 O 3 as cathode electrocatalyst showed a relatively better performance.The maximal power density of 76.2 mW/cm 2 was obtained at the cell voltage of 0.52 V.

Effect of Oxidizing Atmosphere on the Surface of Titanium Dental Implant Material

Direct oxidation is a simple and effective method for titanium surface treatment.In this research,a titanium sample was directly oxidized at the high temperature in two different atmospheres,air and pure oxygen,to obtain better atmosphere for titanium surface treatment.The results of the Raman spectroscopy indicated that in both atmospheres,the rutile bioactive phase(TiO2)has been formed on the titanium surface.The results of X-ray diffraction(XRD)also revealed that the surface of oxygen-treated sample was composed of the rutile phase and titanium monoxide(TiO),while at the surface of the air-treated sample,the rutile phase and titanium dioxide had been formed.Further,the results of Field Emission Scanning Electron Microscopy(FE-SEM)showed that by the surface treatment of titanium in both atmospheres,some micro-features including cracks thinner than 30 nm were formed on the surface.Because of more apatite forming ability and fewer water contact angle and more L-929 cell attachment of the air-treated titanium,it seemed that air,in comparison to the pure oxygen,is more promising atmosphere for the direct oxidation of titanium and improving its biofunctionalization.