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 t...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.展开更多
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...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.展开更多
The direct oxidation of methane(CH_(4))into high-valued C1 oxygenates production has garnered increased attention in effectively using vast CH_(4)and alleviating the global energy crisis.However,due to the high cleava...The direct oxidation of methane(CH_(4))into high-valued C1 oxygenates production has garnered increased attention in effectively using vast CH_(4)and alleviating the global energy crisis.However,due to the high cleavage energy of C—H bond and low polarity of CH_(4)molecule,it is difficult to activate the first C—H bond.Furthermore,C1 oxygenates are readily inclined to be oxidized to CO_(2),because their weaker C—H bond comparing with CH_(4)molecule,resulting in poor selectivity.Herein,we designed ultrathin PdxAuy alloy NWs supported on ZSM-5(Z-5)to investigate the direct oxidation of CH_(4)to high value-added oxygenate under mild conditions.By precisely adjusting the molar ratio of Pd/Au and alloying degree,Pd9Au1NWs/Z-5 showed an excellent yield of 11.57 mmol·g^(–1)·h^(–1)and the outstanding selectivity of 95.1%for C1 oxygenates(CH_(3)OH,CH_(3)OOH and HCOOH).The in-situ spectroscopic and mechanism analysis proved that the enhanced catalytic performance of Pd_(9)Au_(1)NWs/Z-5 was ascribed to the stable one-dimensional nanostructure and the strong synergy effect with high alloying PdAu,which could increase the adsorption capacity of CH_(4)molecules on Pd atoms to promote the CH_(4)conversion.This work offers valuable insights into the design concept of high-efficient catalysts and the structure-activity relationship for the direct oxidation of CH_(4).展开更多
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 w...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.展开更多
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 ex...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...展开更多
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...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.展开更多
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 microsco...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.展开更多
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 direc...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.展开更多
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 p...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.展开更多
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 ...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.展开更多
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...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.展开更多
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 expe...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.展开更多
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 tran...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.展开更多
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 bla...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.展开更多
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...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.展开更多
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...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.展开更多
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 u...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.展开更多
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 lea...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.展开更多
A rhodium-catalyzed[4+3]cycloaddition reaction between N-methoxybenzamides and gem–difluorocyclopropenes is described.The reaction offers a mild and efficient approach towards the synthesis of fluorinated 2 H-azepin-...A rhodium-catalyzed[4+3]cycloaddition reaction between N-methoxybenzamides and gem–difluorocyclopropenes is described.The reaction offers a mild and efficient approach towards the synthesis of fluorinated 2 H-azepin-2-ones with broad substrate scope.A consecutive HOAc-assisted C–N bond formation and fluorine elimination are involved as key steps for success as illustrated by detailed DFT studies.展开更多
基金supported by the Petrochemical Joint Funds of NSFC-CNPC (U1362202)the Postgraduate Innovation Project of China University of Petroleum (East China) (YCXJ2016030)~~
文摘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.
基金supported by the National Defense Science and Technology Industry Nuclear Material Technology Innovation Center Project(No.ICNM-2020-ZH-17)。
文摘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.
基金supported by the Hainan Province Science and Technology Special Fund(ZDYF2024SHFZ074,ZDYF2024SHFZ072)the National Natural Science Foundation of China(22109035,22202053,52164028,52274297,22309037)+4 种基金the Start-up Research Foundation of Hainan University(KYQD(ZR)-20008,20083,20084,21125,23035)the Opening Project of Key Laboratory of Electrochemical Energy Storage and Energy Conversion of Hainan Province(KFKT2021007)the collaborative Innovation Center of Marine Science and Technology,Hainan University(XTCX2022HYC04,XTCX2022HYC05)the Scientific Research Program Funded by Shaanxi Provincial Education Department(Program No.23JK0439)the specific research fund of The Innovation Platform for Academicians of Hainan Province(YSPTZX202315).
文摘The direct oxidation of methane(CH_(4))into high-valued C1 oxygenates production has garnered increased attention in effectively using vast CH_(4)and alleviating the global energy crisis.However,due to the high cleavage energy of C—H bond and low polarity of CH_(4)molecule,it is difficult to activate the first C—H bond.Furthermore,C1 oxygenates are readily inclined to be oxidized to CO_(2),because their weaker C—H bond comparing with CH_(4)molecule,resulting in poor selectivity.Herein,we designed ultrathin PdxAuy alloy NWs supported on ZSM-5(Z-5)to investigate the direct oxidation of CH_(4)to high value-added oxygenate under mild conditions.By precisely adjusting the molar ratio of Pd/Au and alloying degree,Pd9Au1NWs/Z-5 showed an excellent yield of 11.57 mmol·g^(–1)·h^(–1)and the outstanding selectivity of 95.1%for C1 oxygenates(CH_(3)OH,CH_(3)OOH and HCOOH).The in-situ spectroscopic and mechanism analysis proved that the enhanced catalytic performance of Pd_(9)Au_(1)NWs/Z-5 was ascribed to the stable one-dimensional nanostructure and the strong synergy effect with high alloying PdAu,which could increase the adsorption capacity of CH_(4)molecules on Pd atoms to promote the CH_(4)conversion.This work offers valuable insights into the design concept of high-efficient catalysts and the structure-activity relationship for the direct oxidation of CH_(4).
基金the National Natural Science Foundation of China(Nos.21978324 and 22278436)the Science Foundation of China University of Petroleum,Beijing(No.2462021QNXZ009).
文摘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.
基金Project supported by the National Natural Science Foundation of China (50574046, 50774038)the Research Fund for the Doctoral Program of Higher Education of China (20095314120005)+1 种基金the Natural Science Foundation of Yunnan Province (2008E030M) the Foundation of Kun-ming University of Science and Technology (KKZ3200927010)
文摘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...
文摘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.
基金National Natural Science Foundation of China (50372037)Scientific Research Foundations of Shaanxi University of Science and Technology (SUST-B14)
文摘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.
基金Supported by the National Natural Science Foundation of China （50874087 50978212） the Key Projects in the National Science and Technology Pillar Program （2009BAA20B02）
文摘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.
基金Science and Technology Project of Shenzhen,China(No.JCYJ20120617141700417)Natural Science Foundation of Guangdong Province,China(No.2012040007855)
文摘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.
基金financially supported by the National Natural Science Foundation of China (Nos. 51471013, 51571004 and 51404017)
文摘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.
基金Project(2019YFC1907405)supported by the National Key R&D Program of ChinaProject(GJJ200809)supported by the Education Department Project Fund of Jiangxi Province,ChinaProject(2020BAB214021)supported by the Natural Science Foundation of Jiangxi Province,China。
文摘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.
基金Sponsored by the National Natural Science Foundation of China(Grant No.20271019 and 20576027), Natural Science Foundation of Heilongjiang Prov-ince(Grant No.B200504), Postdoctoral Foundationof Heilongjiang Province(Grant No.LBH-Z05066) and Education Department Foundation of Hei-longjiang Province(Grant No.11511270).
文摘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.
基金the NSFC(Nos.21372178 and 21572163)for financial supportsupported by the Scientific Innovation Program for College Students of Zhejiang Province(No. 2016R426061)
文摘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.
基金Funded by National Natural Science Foundation of China(Nos.21376069 and 21576075)Key Project in Hunan Science and Technology Pillar Program(No.2015WK3020)
文摘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.
基金supported by Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry and National Natural Science Foundation of China (20803057)support by the National Self-determined and Innovative Research Funds of WUT
文摘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.
基金Supported by the National Key Basic Research Program of China(2013CB733505,2013CB733501)the National Natural Science Foundation of China(91334202)+2 种基金the Natural Science Foundation of Jiangsu Province of China(BK2012421,BK20130062)the Research Fund for the Doctoral Program of Higher Education of China(20123221120015)the Project for Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘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.
基金support of the experimental tasks for the Savannah River Operations Office under grant No.DE-RP0902SR22229
文摘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.
基金financially supported by the National Basic Research Program of China(Nos.2013CB632601 and 2013CB632604)the National Science Foundation for Distinguished Young Scholars of China(Nos.51125018 and 51504230)+3 种基金the Key Research Program of the Chinese Academy of Sciences(No.KGZD-EW-201-2)the National Natural Science Foundation of China(Nos.51374191,21106167,2160624,and 51104139)the Financial Grant from the China Postdoctoral Science Foundation(Nos.2012M510552 and 2013T60175)the Nonprofit Industry Research Subject of Environmental Projection(No.201509053)
文摘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.
基金National Natural Science Foundation of China(Nos.21861007,21702034)Natural Science Foundation of Guangxi Province(No.2021GXNSFAA075024)+1 种基金“BAGUI Scholar”Program of Guangxi Province of ChinaHigh-Level Innovation Team and Distinguished Scholar Program in Guangxi Colleges and Universities。
文摘A rhodium-catalyzed[4+3]cycloaddition reaction between N-methoxybenzamides and gem–difluorocyclopropenes is described.The reaction offers a mild and efficient approach towards the synthesis of fluorinated 2 H-azepin-2-ones with broad substrate scope.A consecutive HOAc-assisted C–N bond formation and fluorine elimination are involved as key steps for success as illustrated by detailed DFT studies.
