The development of highly active functionalized ionic liquids(ILs)as both extractants and catalysts for use in achieving deep desulfurization continues to pose challenges.In this study,a highly efficient oxidative des...The development of highly active functionalized ionic liquids(ILs)as both extractants and catalysts for use in achieving deep desulfurization continues to pose challenges.In this study,a highly efficient oxidative desulfurization system was constructed,composed of dual-acidic ionic liquids(DILs)and H_(2)O_(2)-AcOH.The investigation results of four DILs prepared from different metal chlorides([HSO_(3)C_(3)NEt_(3)]Cl-MnCl_(n),MnCl_(n)=AlCl_(3),ZnCl_(2),CuCl_(2),FeCl_(3))in oxidative desulfurization showed that[HSO_(3)C_(3)NEt_(3)]Cl-AlCl_(3)had an outstanding catalytic effect and significantly promoted the oxidation of sulfides.With a 0.2 g[HSO_(3)C_(3)NEt_(3)]Cl-AlCl_(3),the removal rate of dibenzothiophene(DBT)reached 100%in 10 mL model oil under mild conditions at 55℃for 20 min.The key is its ability to induce the dismutation of su-peroxide anions(·O_(2)^(-)),which facilitates the generation of singlet oxygen(1 O_(2)).The efficient oxidation of DBT is accomplished through a predominantly^(1)O_(2)-mediated_(n)on-radical mechanism.[HSO_(3)C_(3)NEt_(3)]Cl-AlCl_(3)serves as a favorable medium for contact to be made between^(1)O_(2)and sulfides,which indicates an efficient catalytic-adsorption synergy.展开更多
Development of clean desulfurization process that combines both efficient and environmentally friendly remains a significant challenge for diesel production.The photocatalytic oxidation desulfurization technology is r...Development of clean desulfurization process that combines both efficient and environmentally friendly remains a significant challenge for diesel production.The photocatalytic oxidation desulfurization technology is regarded as a promising process depending on the superior electron transfer and visible light utilization of photocatalyst.Herein,the nonstoichiometry MoO_(3-x)with outstanding photoresponse ability is prepared and modified by imidazole-based ionic liquid[C_(12)mim]Cl to upgrade electronic structure.The interface H-bonding between MoO_(3-x)and[C_(12)mim]Cl regard as electronic transfer channel and the recombination of e^(-)-h^(+)pairs is effectively inhibited with the modification of[C_(12)mim]Cl.Deep desulfurization rate of 96.6%can be reached within 60 min and the MoO_(3-x)/[C_(12)mim]Cl(MoC_(12))photocatalyst demonstrated outstanding cyclic stability within 7 cycles in an extraction coupled photocatalytic oxidation desulfurization(ECPODS)system.The study provides a new perspective on enhancing photocatalytic desulfurization through defect engineering and surface modification.展开更多
In this paper,shorter residence time（a few minutes）with high yield in the trickle bed process for per- acetic acid synthesis by acetaldehyde liquid phase oxidation can be realized on the selected packing material SA...In this paper,shorter residence time（a few minutes）with high yield in the trickle bed process for per- acetic acid synthesis by acetaldehyde liquid phase oxidation can be realized on the selected packing material SA-5118.For acetaldehyde in acetone with ferric ion as catalyst,the optimized process conditions were presented. The main factors influencing the yield,selectivity and conversion are residence time,temperature and acetaldehyde concentration,respectively.The temperature range checked is from 30 to 65℃.High yield of 81.53%with high se- lectivity of 91.84%can be obtained at higher temperature of 55℃when the residence time is 5.5min and the acet- aldehyde concentration is 9.85%（by mass）.And there is a critical acetaldehyde concentration point（Cccp）between 18%and 19.5%（by mass）.At temperature less than 55℃,the highest yield to peracetic acid at each temperature level increases with temperature when the acetaldehyde concentration is below Cccp and decreases with temperature when the acetaldehyde concentration is above Cccp.展开更多
The oxidation of two phase Cu Cr alloys containing 25% and 50% Cr prepared by powder metallurgy (PM) with a rather uniform two phase microstructure has been studied at 700～900 ℃ under oxygen pressure below the stabi...The oxidation of two phase Cu Cr alloys containing 25% and 50% Cr prepared by powder metallurgy (PM) with a rather uniform two phase microstructure has been studied at 700～900 ℃ under oxygen pressure below the stability of the copper oxides. The two PM alloys oxidized very slowly and formed only external Cr 2O 3 scales rather than undergoing an internal oxidation of chromium. This result is attributed mainly to a supply of chromium from the small Cr rich particles dispersed within the Cu rich phase. The oxidation kinetics of the two PM Cu Cr alloys approximately followed the parabolic rate law. The scaling rates are of the same order as those measured for pure chromium under the same oxygen pressure, but smaller than those for the alloys of similar composition prepared by normal arc melting techniques, whose compositions were largely non uniform. The results are interpreted in terms of the two phase nature of these alloys.展开更多
For the goal of sulfur recovery, most methods are aimed at the tail gas with high-concentration H2S, but few effective methods are used for low-concentration H2S. In this work, Low-concentration H2S could be purified ...For the goal of sulfur recovery, most methods are aimed at the tail gas with high-concentration H2S, but few effective methods are used for low-concentration H2S. In this work, Low-concentration H2S could be purified well by liquid phase catalytic oxidation (LCO), and the sulfur resource could also be recovered. The absorption solution was prepared by FeCl3 and sulfosalicylic acid. Under the experimental conditions, the conversion of H2S to S could be maintained above 94% at 60 ℃. In order to enhance the economical efficiency of LCO method, the absorption solution was modified by doping Ce, and a series of experiments were designed to investigate its performance. The results showed that the conversion of H2S had no obvious improvement, but above 98% conversion could be gained at 60 ℃, and the H2S conversion rate was enhanced. The optimum addition quality of Ce(NO3)3 was 0.08 g to 50 ml Fe3+ solution.展开更多
In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were...In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were obtained from a combination of experimental observation and hypothetical models. The results clearly showed that both the oxidation rate of toluene and generation rate of the aromatic product were proportional to the concentration of the substrate, the partial pressure of oxygen and the surface area of the catalyst. The energy barrier of toluene oxidation to benzyl alcohol was the highest(≈ 81 kJ mol^(-1)), while that of benzyl alcohol oxidation to benzaldehyde was the lowest(≈ 57 kJ mol^(-1)). Moreover, the activation energy of further oxidation of benzaldehyde in an acetic acid solvent was only slightly lower(≈ 1.9 kJ mol^(-1)) than that of toluene oxidation. Significantly, the transformation of benzyl alcohol indeed contributed to the generation of benzaldehyde and this step conformed to a first-order parallel-consecutive model. Increased reaction temperature and residence time favored the transformation of benzyl alcohol to benzaldehyde. In addition, doping with molybdenum at Mn/Mo = 3/1 enhanced the catalytic performance of the heterogeneous catalyst and was attributed to the presence of a synergetic effect between different metal cations. Regarding the microscopic kinetics, the LH-OS-ND mechanism(Langmuir–Hinshelwood adsorption of reagents on the same type of active sites and non-dissociative adsorption of oxygen) was verified as responsible for the heterogeneous oxidation of toluene. Oxygen and benzaldehyde were weakly adsorbed(Δ H_(ads,Oxy) ≈^(-1)5 kJ mol^(-1), Δ H _(ads)0,Bald) ≈-30 kJ mol^(-1)), but showed strong mobility(Δ S_(ads,Oxy) ≈-22 J mol^(-1) K^(-1)), Δ S_(ads,Bald) ≈-39 J mol^(-1) K^(-1)). The fundamental intrinsic rates were deduced based on the LH-OS-ND mechanism and showed great consistency with the macroscopic results.展开更多
In this paper, a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed. The effects of the reaction tempe...In this paper, a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed. The effects of the reaction temperature, catalyst concentration and ratio of catalyst on the lime evolution of the experimental concentration for the constituents including raw material, intermediates and product are investigated. The model parameters are determined in a nonlinear optimization, minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a semi-batch oxidation reactor where the gas and liquid phase were well nuxed. The kinetics data demonstrate that the model is suitable to the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid.展开更多
Catalytic activity and selectivity of prepared catalysts (Fe2O3/ and Fe2O3/AC(KOH)) were investigated for liquid phase aerobic oxidation of primary and secondary alcohols, in a batch reactor, using solvent free condit...Catalytic activity and selectivity of prepared catalysts (Fe2O3/ and Fe2O3/AC(KOH)) were investigated for liquid phase aerobic oxidation of primary and secondary alcohols, in a batch reactor, using solvent free condition and/or eco-friendly solvents. The catalysts were characterized by SEM, EDX, XRD, FTIR, TGA/DTA, and surface area and pore size analysis. Experimental data revealed that Fe2O3/AC(KOH) was an efficient catalyst for the oxidation (dehydrogenation) of alcohol while was found to show catalytic activity for both dehydration and dehydrogenation of alcohols. The catalysts were recycled by simple filtration, and used several times without any loss of catalytic activity.展开更多
Pt/CeO2–ZrO2–SnO2/γ-Al2O3 catalysts were prepared by co-precipitation and wet impregnation methods for catalytic oxidation of acetaldehyde to acetic acid in water. In the present catalysts, Pt and CeO2–ZrO2–SnO2 ...Pt/CeO2–ZrO2–SnO2/γ-Al2O3 catalysts were prepared by co-precipitation and wet impregnation methods for catalytic oxidation of acetaldehyde to acetic acid in water. In the present catalysts, Pt and CeO2–ZrO2–SnO2 were successfully dispersed on the γ-Al2O3 support.Dependences of platinum content and reaction time on the selective oxidation of acetaldehyde to acetic acid were investigated to optimize the reaction conditions for obtaining both high acetaldehyde conversion and highest selectivity to acetic acid. Among the catalysts, a Pt（6.4 wt.%）/Ce0.68Zr0.17Sn0.15O2.0（16 wt.%）/γ-Al2O3 catalyst showed the highest acetaldehyde oxidation activity. On this catalyst, acetaldehyde was completely oxidized after the reaction at 0°C for 8 hr, and the selectivity to acetic acid reached to 95%and higher after the reaction for 4 hr and longer.展开更多
The selective oxidation of methanol to methyl formate is one of the most attractive processes to obtain value-added methanol-downstream products.The development of highly efficient and stable catalysts is critical for...The selective oxidation of methanol to methyl formate is one of the most attractive processes to obtain value-added methanol-downstream products.The development of highly efficient and stable catalysts is critical for this transformation.In this study,a series of MIL-88B(Fe_(x),Co_(1‒x))bimetallic catalysts with different Fe/Co molar ratios were prepared through a one-pot hydrothermal method.X-ray diffraction,scanning electron microscopy,high-resolution transmission electron microscopy,energy dispersive spectroscopy,Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy,N2 adsorption-desorption,and inductively coupled plasma-mass spectrometry characterization were performed to elucidate the structure of the catalysts.The activity of the catalysts were assessed in the one-step oxidation of methanol to methyl formate with H_(2)O_(2)in a liquid-phase batch reactor.The results show that the MIL-88B(Fe_(x),Co_(1‒x))catalysts exhibit uniform needle-like morphologies with an average length and width of 400-600 nm and 100-150 nm,respectively.Co^(2+)is incorporated into the framework by partially replacing Fe^(3+)in MIL-88B.Moreover,the catalyst efficiently promoted the conversion of methanol to methyl formate.When MIL-88B(Fe_(0.7),Co_(0.3))catalyst was used with a molar ratio of H_(2)O_(2)to methanol of 0.5 at 80℃for 60 min,34.8%methanol conversion was achieved,and the selectivity toward methyl formate was 67.6%.The catalysts also showed great stability with a steady conversion and selectivity even after four cycles.The preliminary oxidation mechanism was also studied.It was determined that H_(2)O_(2)is first adsorbed on the Fe^(3+)sites and subsequently activates these sites.Methanol is adsorbed by the O atoms of the framework through hydrogen bonding and is gradually oxidized to formic acid.Subsequently,formic acid reacts with the residual methanol at the Fe^(3+)and Co^(2+)Lewis acid sites to form methyl formate.展开更多
Hydrogen sulfide in rural biogas was removed with liquid-phase catalytic oxidation.By using rare earth as catalyst,and sulfosalicylic acid as stabilizer,H2S purification efficiency could increase as high as 96%,and su...Hydrogen sulfide in rural biogas was removed with liquid-phase catalytic oxidation.By using rare earth as catalyst,and sulfosalicylic acid as stabilizer,H2S purification efficiency could increase as high as 96%,and sulfur capacity of the composite solution was about 3 g/L.The results show that purification efficiency was affected by catalyst addition,pH,experimental temperature,and sulfur capacity.The parameters effects on catalytic oxidation were studied,and the optimized conditions were that Fe3+ concentration 0.08 mg/L,reaction temperature 70°C,pH 9.0,with a absorption solution volume of 50 mL,a gas flow rate 200 mL/min,and H2S mass concentration of 1.58-2.02 mg/m3.展开更多
A few factors affecting plasma oxidation desulfurization of ethyl- thioether were investigated.Under the typical conditions,the conversion and degree of desulfurization of ethyl-thioether can be achieved up to 88% and...A few factors affecting plasma oxidation desulfurization of ethyl- thioether were investigated.Under the typical conditions,the conversion and degree of desulfurization of ethyl-thioether can be achieved up to 88% and 79% respectively.展开更多
Understanding the crystal phase evolution of bimetallic oxide anodes is the main concern to profoundly reveal the conversion reaction kinetics and sodium-ion storage mechanisms.Herein,an integrated selfsupporting anod...Understanding the crystal phase evolution of bimetallic oxide anodes is the main concern to profoundly reveal the conversion reaction kinetics and sodium-ion storage mechanisms.Herein,an integrated selfsupporting anode of the Cu-decorated Cu-Mn bimetallic oxides with oxygen vacancies(Ov-BMO-Cu)are in-situ generated by phase separation and hydrogen etching using nanoporous Cu-Mn alloy as selfsacrificial templates.On this basis,we have elucidated the relationship between the phase evolution,oxygen vacancies and sodium-ion storage mechanisms,further demonstrating the evolution of oxygen vacancies and the inhibition effect of manganese oxides as an“anchor”on grain aggregation of copper oxides.The kinetic analyses confirm that the expanded lattice space and increased oxygen vacancies of cycled Ov-BMO-Cu synergistically guarantee effective sodium-ion diffusion and storage mechanisms.Therefore,the Ov-BMO-Cu electrode exhibits higher reversible capacities of 4.04 mA h cm^(-2)at 0.2 mA cm^(-2)after 100 cycles and 2.20 m A h cm^(-2)at 1.0 mA cm^(-2)after 500 cycles.Besides,the presodiated Ov-BMO-Cu anode delivers a considerable reversible capacity of 0.79 m A h cm^(-2)at 1.0 mA cm^(-2)after 60 cycles in full cells with Na_(3)V_(2)(PO_(4))_(3)cathode,confirming its outstanding practicality.Thus,this work is expected to provide enlightenment for designing high-capacity bimetallic oxide anodes.展开更多
Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions dur...Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions during anionic redox reactions lead to poor electrochemical performance with sluggish kinetics.Here, we propose a synergy of Li-Cu cations in harnessing the full potential of oxygen redox, through Li displacement and suppressed phase transition in P3-type layered oxide cathode. P3-type Na_(0.7)[Li_(0.1)Cu_(0.2)Mn_(0.7)]O_(2) cathode delivers a large specific capacity of ~212 mA h g^(-1)at 15 mA g^(-1). The discharge capacity is maintained up to ~90% of the initial capacity after 100 cycles, with stable occurrence of the oxygen redox in the high-voltage region. Through advanced experimental analyses and first-principles calculations, it is confirmed that a stepwise redox reaction based on Cu and O ions occurs for the charge-compensation mechanism upon charging. Based on a concrete understanding of the reaction mechanism, the Li displacement by the synergy of Li-Cu cations plays a crucial role in suppressing the structural change of the P3-type layered material under the oxygen redox reaction, and it is expected to be an effective strategy for stabilizing the oxygen redox in the layered oxides of Na-ion batteries.展开更多
In this paper, two microwave irradiation methods：（i） liquid-phase microwave irradiation（MWI） reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and（ii...In this paper, two microwave irradiation methods：（i） liquid-phase microwave irradiation（MWI） reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and（ii） solid-phase MWI reduction of graphite oxide powder have been successfully carried out to reduce graphite oxide. The reduced graphene oxide products are thoroughly characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectral analysis, Raman spectroscopy, UV-Vis absorption spectral analysis,and four-point probe conductivity measurements. The results show that both methods can efficiently remove the oxygencontaining functional groups attached to the graphite layers, though the solid-phase MWI reduction method can obtain far more efficiently a higher quality-reduced graphene oxide with fewer defects. The I（D）/I（G） ratio of the solid-phase MWI sample is as low as 0.46, which is only half of that of the liquid-phase MWI samples. The electrical conductivity of the reduced graphene oxide by the solid method reaches 747.9 S/m, which is about 25 times higher than that made by the liquid-phase method.展开更多
This paper describes the design of a FeWO_(x)-based oxygen carrier for the chemical partial oxidation of methane(CLPOM).Thermodynamic screening and kinetic analyses both forecast the FeWO_(x)-based oxygen carrier as a...This paper describes the design of a FeWO_(x)-based oxygen carrier for the chemical partial oxidation of methane(CLPOM).Thermodynamic screening and kinetic analyses both forecast the FeWO_(x)-based oxygen carrier as a promising candidate for the production of syngas.The total methane conversion and syngas yield can be dramatically increased with this catalyst compared to the case with the unmodified WO_(3)/SiO_(2),thereby enabling CLPOM with 62%methane conversion,93%CO gas-phase selectivity,94%H2 selectivity,and a 2.4 H_(2)/CO ratio.The catalyst has the advantages of high availability of lattice oxygen to oxidize carbonaceous intermediates in time,together with the formation of an Fe-W alloy to promote the surface reaction.Consequently,it demonstrates excellent catalytic performance with no catalyst deactivation at 900℃ and 1 atm.The excellent structural stability plays an essential role in CLPOM.As revealed via XPS and ICP,the phase segregation has not been observed due to the strong interaction between Fe and W,which resulted in the formation of the Fe-W alloy during the reduction processes and the match between the ion oxidation rates of the Fe and W ions in the oxidation stage.The results provide fundamental information on the reaction mechanism of FeWO_(x)/SiO_(2),and present it as a promising candidate for CLPOM.展开更多
Methane chemistry is one of the“Holy Grails of catalysis”.It is highly desirable but challenge to transform methane into value-added chemicals,because of its high C-H bonding energy(435 kJ/mol),lack ofπbonding or u...Methane chemistry is one of the“Holy Grails of catalysis”.It is highly desirable but challenge to transform methane into value-added chemicals,because of its high C-H bonding energy(435 kJ/mol),lack ofπbonding or unpaired electrons.Currently,commercial methane conversion is usually carried out in harsh conditions with enormous energy input.Photocatalytic partial oxidation of methane to liquid oxygenates(PPOMO)is a future-oriented technology towards realizing high efficiency and high selectivity under mild conditions.The selection of oxidant is crucial to the PPOMO performance.Hence,attentions are paid to the research progress of PPOMO with various oxidants(O_(2),H_(2)O,H_(2)O_(2)and other oxidants).Moreover,the activation of the selected oxidants is also highly emphasized.Meanwhile,we summarized the methane activation mechanisms focusing on the C-H bond that was broken mainly by·OH radical,O-specie or photogenerated hole(h+).Finally,the challenges and prospects in this subject are briefly discussed.展开更多
The internal oxidation behavior of Pd-40Ag-1RE (RE = Sm, Eu, Gd, Y) alloy wires has been studied in air at 800 °C 1200°C. The dependence of internal oxidation depth ξ on reaction time t can be expressed as ...The internal oxidation behavior of Pd-40Ag-1RE (RE = Sm, Eu, Gd, Y) alloy wires has been studied in air at 800 °C 1200°C. The dependence of internal oxidation depth ξ on reaction time t can be expressed as ξ = Ktn, the reaction index n = 0.50 approximately 0.75. The higher the oxidation temperature is, the larger the n value is. It means that the internal oxidation of wire sampls at high temperature deviates from parabola rule observed on plate sample. The activation energies of the studied alloys range over 120 approximately 160 kJ/mol. The internal oxidation process is controlled by the bulk diffusion of oxygen.展开更多
The presence of excess Ta in high-temperature protective coatings can compromise the integrity of the Al_(2)O_(3)scale on the surface,which has a negative impact on the oxidation behavior and reduces the service life....The presence of excess Ta in high-temperature protective coatings can compromise the integrity of the Al_(2)O_(3)scale on the surface,which has a negative impact on the oxidation behavior and reduces the service life.The effects of oxygen doping on the isothermal oxidation of three sputtered nanocrystalline coatings were investigated at 1100°C.The results indicated that oxygen doping inhibited the diffusion of Ta from the coating to the oxide scale,which was primarily attributed to the preferential oxidation of the Al in the coating.However,excess oxygen doping decreased the amount of Al available for the formation of the Al_(2)O_(3)scale on the coating,thus reducing the inhibitory effect on Ta oxidation.Moreover,doping with excess O caused spalling of the oxide scale.Therefore,the right balance in O doping is crucial for suppressing Ta oxidation while maintaining the integrity of the oxide scale.展开更多
Iron oxide nanoparticles were synthesized by precipitation method and supported on activated carbon. The catalyst thus obtained was characterized by various physicochemical techniques, and used for the liquid phase de...Iron oxide nanoparticles were synthesized by precipitation method and supported on activated carbon. The catalyst thus obtained was characterized by various physicochemical techniques, and used for the liquid phase dehydrogenation/oxidation of octanol in a batch reactor at various temperatures in the range 30 °C - 60 °C. Maximum conversion of octanol to octanal was attained at 60°C in 30 min. However, with longer reaction time, the selectivity of the catalyst was found to change in favor of octene as a product. The catalyst could be recovered and reused multiple times without any decline in its catalytic performance.展开更多
基金support provided by South Africa National Research Foundation(UID 95983,113648,137947)Foundation for Innovative Research Groups of the Natural Science Foundation of Hebei Province(no.B2021208005).
文摘The development of highly active functionalized ionic liquids(ILs)as both extractants and catalysts for use in achieving deep desulfurization continues to pose challenges.In this study,a highly efficient oxidative desulfurization system was constructed,composed of dual-acidic ionic liquids(DILs)and H_(2)O_(2)-AcOH.The investigation results of four DILs prepared from different metal chlorides([HSO_(3)C_(3)NEt_(3)]Cl-MnCl_(n),MnCl_(n)=AlCl_(3),ZnCl_(2),CuCl_(2),FeCl_(3))in oxidative desulfurization showed that[HSO_(3)C_(3)NEt_(3)]Cl-AlCl_(3)had an outstanding catalytic effect and significantly promoted the oxidation of sulfides.With a 0.2 g[HSO_(3)C_(3)NEt_(3)]Cl-AlCl_(3),the removal rate of dibenzothiophene(DBT)reached 100%in 10 mL model oil under mild conditions at 55℃for 20 min.The key is its ability to induce the dismutation of su-peroxide anions(·O_(2)^(-)),which facilitates the generation of singlet oxygen(1 O_(2)).The efficient oxidation of DBT is accomplished through a predominantly^(1)O_(2)-mediated_(n)on-radical mechanism.[HSO_(3)C_(3)NEt_(3)]Cl-AlCl_(3)serves as a favorable medium for contact to be made between^(1)O_(2)and sulfides,which indicates an efficient catalytic-adsorption synergy.
基金supports from National Natural Science Foundation of China(Nos.22172066,22378176)supported by State Key Laboratory of Heavy Oil Processing.Supported by Jiangsu Collaborative Innovation Center of TechnologyMaterial of Water Treatment,Suzhou University of Science and Technology.
文摘Development of clean desulfurization process that combines both efficient and environmentally friendly remains a significant challenge for diesel production.The photocatalytic oxidation desulfurization technology is regarded as a promising process depending on the superior electron transfer and visible light utilization of photocatalyst.Herein,the nonstoichiometry MoO_(3-x)with outstanding photoresponse ability is prepared and modified by imidazole-based ionic liquid[C_(12)mim]Cl to upgrade electronic structure.The interface H-bonding between MoO_(3-x)and[C_(12)mim]Cl regard as electronic transfer channel and the recombination of e^(-)-h^(+)pairs is effectively inhibited with the modification of[C_(12)mim]Cl.Deep desulfurization rate of 96.6%can be reached within 60 min and the MoO_(3-x)/[C_(12)mim]Cl(MoC_(12))photocatalyst demonstrated outstanding cyclic stability within 7 cycles in an extraction coupled photocatalytic oxidation desulfurization(ECPODS)system.The study provides a new perspective on enhancing photocatalytic desulfurization through defect engineering and surface modification.
文摘In this paper,shorter residence time（a few minutes）with high yield in the trickle bed process for per- acetic acid synthesis by acetaldehyde liquid phase oxidation can be realized on the selected packing material SA-5118.For acetaldehyde in acetone with ferric ion as catalyst,the optimized process conditions were presented. The main factors influencing the yield,selectivity and conversion are residence time,temperature and acetaldehyde concentration,respectively.The temperature range checked is from 30 to 65℃.High yield of 81.53%with high se- lectivity of 91.84%can be obtained at higher temperature of 55℃when the residence time is 5.5min and the acet- aldehyde concentration is 9.85%（by mass）.And there is a critical acetaldehyde concentration point（Cccp）between 18%and 19.5%（by mass）.At temperature less than 55℃,the highest yield to peracetic acid at each temperature level increases with temperature when the acetaldehyde concentration is below Cccp and decreases with temperature when the acetaldehyde concentration is above Cccp.
文摘The oxidation of two phase Cu Cr alloys containing 25% and 50% Cr prepared by powder metallurgy (PM) with a rather uniform two phase microstructure has been studied at 700～900 ℃ under oxygen pressure below the stability of the copper oxides. The two PM alloys oxidized very slowly and formed only external Cr 2O 3 scales rather than undergoing an internal oxidation of chromium. This result is attributed mainly to a supply of chromium from the small Cr rich particles dispersed within the Cu rich phase. The oxidation kinetics of the two PM Cu Cr alloys approximately followed the parabolic rate law. The scaling rates are of the same order as those measured for pure chromium under the same oxygen pressure, but smaller than those for the alloys of similar composition prepared by normal arc melting techniques, whose compositions were largely non uniform. The results are interpreted in terms of the two phase nature of these alloys.
基金the Natural Science Foundation of Yunnan Province (2001E0011Q)the Science Foundation of The Education Department of Yunnan Province (0142111 and 07Z11402)
文摘For the goal of sulfur recovery, most methods are aimed at the tail gas with high-concentration H2S, but few effective methods are used for low-concentration H2S. In this work, Low-concentration H2S could be purified well by liquid phase catalytic oxidation (LCO), and the sulfur resource could also be recovered. The absorption solution was prepared by FeCl3 and sulfosalicylic acid. Under the experimental conditions, the conversion of H2S to S could be maintained above 94% at 60 ℃. In order to enhance the economical efficiency of LCO method, the absorption solution was modified by doping Ce, and a series of experiments were designed to investigate its performance. The results showed that the conversion of H2S had no obvious improvement, but above 98% conversion could be gained at 60 ℃, and the H2S conversion rate was enhanced. The optimum addition quality of Ce(NO3)3 was 0.08 g to 50 ml Fe3+ solution.
基金supported by the National Natural Science Foundation of China (No. 21376163)
文摘In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were obtained from a combination of experimental observation and hypothetical models. The results clearly showed that both the oxidation rate of toluene and generation rate of the aromatic product were proportional to the concentration of the substrate, the partial pressure of oxygen and the surface area of the catalyst. The energy barrier of toluene oxidation to benzyl alcohol was the highest(≈ 81 kJ mol^(-1)), while that of benzyl alcohol oxidation to benzaldehyde was the lowest(≈ 57 kJ mol^(-1)). Moreover, the activation energy of further oxidation of benzaldehyde in an acetic acid solvent was only slightly lower(≈ 1.9 kJ mol^(-1)) than that of toluene oxidation. Significantly, the transformation of benzyl alcohol indeed contributed to the generation of benzaldehyde and this step conformed to a first-order parallel-consecutive model. Increased reaction temperature and residence time favored the transformation of benzyl alcohol to benzaldehyde. In addition, doping with molybdenum at Mn/Mo = 3/1 enhanced the catalytic performance of the heterogeneous catalyst and was attributed to the presence of a synergetic effect between different metal cations. Regarding the microscopic kinetics, the LH-OS-ND mechanism(Langmuir–Hinshelwood adsorption of reagents on the same type of active sites and non-dissociative adsorption of oxygen) was verified as responsible for the heterogeneous oxidation of toluene. Oxygen and benzaldehyde were weakly adsorbed(Δ H_(ads,Oxy) ≈^(-1)5 kJ mol^(-1), Δ H _(ads)0,Bald) ≈-30 kJ mol^(-1)), but showed strong mobility(Δ S_(ads,Oxy) ≈-22 J mol^(-1) K^(-1)), Δ S_(ads,Bald) ≈-39 J mol^(-1) K^(-1)). The fundamental intrinsic rates were deduced based on the LH-OS-ND mechanism and showed great consistency with the macroscopic results.
文摘In this paper, a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed. The effects of the reaction temperature, catalyst concentration and ratio of catalyst on the lime evolution of the experimental concentration for the constituents including raw material, intermediates and product are investigated. The model parameters are determined in a nonlinear optimization, minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a semi-batch oxidation reactor where the gas and liquid phase were well nuxed. The kinetics data demonstrate that the model is suitable to the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid.
文摘Catalytic activity and selectivity of prepared catalysts (Fe2O3/ and Fe2O3/AC(KOH)) were investigated for liquid phase aerobic oxidation of primary and secondary alcohols, in a batch reactor, using solvent free condition and/or eco-friendly solvents. The catalysts were characterized by SEM, EDX, XRD, FTIR, TGA/DTA, and surface area and pore size analysis. Experimental data revealed that Fe2O3/AC(KOH) was an efficient catalyst for the oxidation (dehydrogenation) of alcohol while was found to show catalytic activity for both dehydration and dehydrogenation of alcohols. The catalysts were recycled by simple filtration, and used several times without any loss of catalytic activity.
文摘Pt/CeO2–ZrO2–SnO2/γ-Al2O3 catalysts were prepared by co-precipitation and wet impregnation methods for catalytic oxidation of acetaldehyde to acetic acid in water. In the present catalysts, Pt and CeO2–ZrO2–SnO2 were successfully dispersed on the γ-Al2O3 support.Dependences of platinum content and reaction time on the selective oxidation of acetaldehyde to acetic acid were investigated to optimize the reaction conditions for obtaining both high acetaldehyde conversion and highest selectivity to acetic acid. Among the catalysts, a Pt（6.4 wt.%）/Ce0.68Zr0.17Sn0.15O2.0（16 wt.%）/γ-Al2O3 catalyst showed the highest acetaldehyde oxidation activity. On this catalyst, acetaldehyde was completely oxidized after the reaction at 0°C for 8 hr, and the selectivity to acetic acid reached to 95%and higher after the reaction for 4 hr and longer.
文摘The selective oxidation of methanol to methyl formate is one of the most attractive processes to obtain value-added methanol-downstream products.The development of highly efficient and stable catalysts is critical for this transformation.In this study,a series of MIL-88B(Fe_(x),Co_(1‒x))bimetallic catalysts with different Fe/Co molar ratios were prepared through a one-pot hydrothermal method.X-ray diffraction,scanning electron microscopy,high-resolution transmission electron microscopy,energy dispersive spectroscopy,Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy,N2 adsorption-desorption,and inductively coupled plasma-mass spectrometry characterization were performed to elucidate the structure of the catalysts.The activity of the catalysts were assessed in the one-step oxidation of methanol to methyl formate with H_(2)O_(2)in a liquid-phase batch reactor.The results show that the MIL-88B(Fe_(x),Co_(1‒x))catalysts exhibit uniform needle-like morphologies with an average length and width of 400-600 nm and 100-150 nm,respectively.Co^(2+)is incorporated into the framework by partially replacing Fe^(3+)in MIL-88B.Moreover,the catalyst efficiently promoted the conversion of methanol to methyl formate.When MIL-88B(Fe_(0.7),Co_(0.3))catalyst was used with a molar ratio of H_(2)O_(2)to methanol of 0.5 at 80℃for 60 min,34.8%methanol conversion was achieved,and the selectivity toward methyl formate was 67.6%.The catalysts also showed great stability with a steady conversion and selectivity even after four cycles.The preliminary oxidation mechanism was also studied.It was determined that H_(2)O_(2)is first adsorbed on the Fe^(3+)sites and subsequently activates these sites.Methanol is adsorbed by the O atoms of the framework through hydrogen bonding and is gradually oxidized to formic acid.Subsequently,formic acid reacts with the residual methanol at the Fe^(3+)and Co^(2+)Lewis acid sites to form methyl formate.
基金Project(2008ZX07105-002) supported by the Erhai Lake Project of National Science and Technology Major Project in the 11th Five years Plan of China
文摘Hydrogen sulfide in rural biogas was removed with liquid-phase catalytic oxidation.By using rare earth as catalyst,and sulfosalicylic acid as stabilizer,H2S purification efficiency could increase as high as 96%,and sulfur capacity of the composite solution was about 3 g/L.The results show that purification efficiency was affected by catalyst addition,pH,experimental temperature,and sulfur capacity.The parameters effects on catalytic oxidation were studied,and the optimized conditions were that Fe3+ concentration 0.08 mg/L,reaction temperature 70°C,pH 9.0,with a absorption solution volume of 50 mL,a gas flow rate 200 mL/min,and H2S mass concentration of 1.58-2.02 mg/m3.
基金The project was supported by National Natural Science Foundation of China
文摘A few factors affecting plasma oxidation desulfurization of ethyl- thioether were investigated.Under the typical conditions,the conversion and degree of desulfurization of ethyl-thioether can be achieved up to 88% and 79% respectively.
基金supported by the Natural Science Foundation of China(5207123251871165)。
文摘Understanding the crystal phase evolution of bimetallic oxide anodes is the main concern to profoundly reveal the conversion reaction kinetics and sodium-ion storage mechanisms.Herein,an integrated selfsupporting anode of the Cu-decorated Cu-Mn bimetallic oxides with oxygen vacancies(Ov-BMO-Cu)are in-situ generated by phase separation and hydrogen etching using nanoporous Cu-Mn alloy as selfsacrificial templates.On this basis,we have elucidated the relationship between the phase evolution,oxygen vacancies and sodium-ion storage mechanisms,further demonstrating the evolution of oxygen vacancies and the inhibition effect of manganese oxides as an“anchor”on grain aggregation of copper oxides.The kinetic analyses confirm that the expanded lattice space and increased oxygen vacancies of cycled Ov-BMO-Cu synergistically guarantee effective sodium-ion diffusion and storage mechanisms.Therefore,the Ov-BMO-Cu electrode exhibits higher reversible capacities of 4.04 mA h cm^(-2)at 0.2 mA cm^(-2)after 100 cycles and 2.20 m A h cm^(-2)at 1.0 mA cm^(-2)after 500 cycles.Besides,the presodiated Ov-BMO-Cu anode delivers a considerable reversible capacity of 0.79 m A h cm^(-2)at 1.0 mA cm^(-2)after 60 cycles in full cells with Na_(3)V_(2)(PO_(4))_(3)cathode,confirming its outstanding practicality.Thus,this work is expected to provide enlightenment for designing high-capacity bimetallic oxide anodes.
基金supported by the National Research Foundation of Korea grant funded by the Korea government (NRF2021R1A2C1014280)the Fundamental Research Program of the Korea Institute of Material Science (PNK9370)。
文摘Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions during anionic redox reactions lead to poor electrochemical performance with sluggish kinetics.Here, we propose a synergy of Li-Cu cations in harnessing the full potential of oxygen redox, through Li displacement and suppressed phase transition in P3-type layered oxide cathode. P3-type Na_(0.7)[Li_(0.1)Cu_(0.2)Mn_(0.7)]O_(2) cathode delivers a large specific capacity of ~212 mA h g^(-1)at 15 mA g^(-1). The discharge capacity is maintained up to ~90% of the initial capacity after 100 cycles, with stable occurrence of the oxygen redox in the high-voltage region. Through advanced experimental analyses and first-principles calculations, it is confirmed that a stepwise redox reaction based on Cu and O ions occurs for the charge-compensation mechanism upon charging. Based on a concrete understanding of the reaction mechanism, the Li displacement by the synergy of Li-Cu cations plays a crucial role in suppressing the structural change of the P3-type layered material under the oxygen redox reaction, and it is expected to be an effective strategy for stabilizing the oxygen redox in the layered oxides of Na-ion batteries.
基金Project supported by the National Natural Science Foundation of China(Grant No.61176090)the National Science and Technology Project 02,China(Grant No.2013ZX02303-004)
文摘In this paper, two microwave irradiation methods：（i） liquid-phase microwave irradiation（MWI） reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and（ii） solid-phase MWI reduction of graphite oxide powder have been successfully carried out to reduce graphite oxide. The reduced graphene oxide products are thoroughly characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectral analysis, Raman spectroscopy, UV-Vis absorption spectral analysis,and four-point probe conductivity measurements. The results show that both methods can efficiently remove the oxygencontaining functional groups attached to the graphite layers, though the solid-phase MWI reduction method can obtain far more efficiently a higher quality-reduced graphene oxide with fewer defects. The I（D）/I（G） ratio of the solid-phase MWI sample is as low as 0.46, which is only half of that of the liquid-phase MWI samples. The electrical conductivity of the reduced graphene oxide by the solid method reaches 747.9 S/m, which is about 25 times higher than that made by the liquid-phase method.
文摘This paper describes the design of a FeWO_(x)-based oxygen carrier for the chemical partial oxidation of methane(CLPOM).Thermodynamic screening and kinetic analyses both forecast the FeWO_(x)-based oxygen carrier as a promising candidate for the production of syngas.The total methane conversion and syngas yield can be dramatically increased with this catalyst compared to the case with the unmodified WO_(3)/SiO_(2),thereby enabling CLPOM with 62%methane conversion,93%CO gas-phase selectivity,94%H2 selectivity,and a 2.4 H_(2)/CO ratio.The catalyst has the advantages of high availability of lattice oxygen to oxidize carbonaceous intermediates in time,together with the formation of an Fe-W alloy to promote the surface reaction.Consequently,it demonstrates excellent catalytic performance with no catalyst deactivation at 900℃ and 1 atm.The excellent structural stability plays an essential role in CLPOM.As revealed via XPS and ICP,the phase segregation has not been observed due to the strong interaction between Fe and W,which resulted in the formation of the Fe-W alloy during the reduction processes and the match between the ion oxidation rates of the Fe and W ions in the oxidation stage.The results provide fundamental information on the reaction mechanism of FeWO_(x)/SiO_(2),and present it as a promising candidate for CLPOM.
基金the National Key R&D Program of China(No.2021YFA1500800)National Natural Science Foundation of China(No.22072106).
文摘Methane chemistry is one of the“Holy Grails of catalysis”.It is highly desirable but challenge to transform methane into value-added chemicals,because of its high C-H bonding energy(435 kJ/mol),lack ofπbonding or unpaired electrons.Currently,commercial methane conversion is usually carried out in harsh conditions with enormous energy input.Photocatalytic partial oxidation of methane to liquid oxygenates(PPOMO)is a future-oriented technology towards realizing high efficiency and high selectivity under mild conditions.The selection of oxidant is crucial to the PPOMO performance.Hence,attentions are paid to the research progress of PPOMO with various oxidants(O_(2),H_(2)O,H_(2)O_(2)and other oxidants).Moreover,the activation of the selected oxidants is also highly emphasized.Meanwhile,we summarized the methane activation mechanisms focusing on the C-H bond that was broken mainly by·OH radical,O-specie or photogenerated hole(h+).Finally,the challenges and prospects in this subject are briefly discussed.
文摘The internal oxidation behavior of Pd-40Ag-1RE (RE = Sm, Eu, Gd, Y) alloy wires has been studied in air at 800 °C 1200°C. The dependence of internal oxidation depth ξ on reaction time t can be expressed as ξ = Ktn, the reaction index n = 0.50 approximately 0.75. The higher the oxidation temperature is, the larger the n value is. It means that the internal oxidation of wire sampls at high temperature deviates from parabola rule observed on plate sample. The activation energies of the studied alloys range over 120 approximately 160 kJ/mol. The internal oxidation process is controlled by the bulk diffusion of oxygen.
基金supported by the National Natural Science Foundation of China under Grant Nos.51671053 and 51801021the Fundamental Research Funds for the Central Universities(No.N2302007)the Ministry of Industry and Information Technology Project(No.MJ-2017-J-99).
文摘The presence of excess Ta in high-temperature protective coatings can compromise the integrity of the Al_(2)O_(3)scale on the surface,which has a negative impact on the oxidation behavior and reduces the service life.The effects of oxygen doping on the isothermal oxidation of three sputtered nanocrystalline coatings were investigated at 1100°C.The results indicated that oxygen doping inhibited the diffusion of Ta from the coating to the oxide scale,which was primarily attributed to the preferential oxidation of the Al in the coating.However,excess oxygen doping decreased the amount of Al available for the formation of the Al_(2)O_(3)scale on the coating,thus reducing the inhibitory effect on Ta oxidation.Moreover,doping with excess O caused spalling of the oxide scale.Therefore,the right balance in O doping is crucial for suppressing Ta oxidation while maintaining the integrity of the oxide scale.
文摘Iron oxide nanoparticles were synthesized by precipitation method and supported on activated carbon. The catalyst thus obtained was characterized by various physicochemical techniques, and used for the liquid phase dehydrogenation/oxidation of octanol in a batch reactor at various temperatures in the range 30 °C - 60 °C. Maximum conversion of octanol to octanal was attained at 60°C in 30 min. However, with longer reaction time, the selectivity of the catalyst was found to change in favor of octene as a product. The catalyst could be recovered and reused multiple times without any decline in its catalytic performance.
