Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a φ48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH...Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a φ48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH3COO)2.4H2O as catalyst.The Co2+ concentration [Co2+] was determined by extraction spectrophotometry and hereby the Co3+ concentration [Co3+] was obtained by mass balance.The results showed that [Co3+] reached the maximum at about 25-30min.[Co3+] increased with increasing Co catalyst amount at total Co concentration<150 mg.L-1 of toluene.The conversion of toluene,yield and selectivity of benzoic acid increased with the increasing [Co3+/Co2+] max.A high [Co3+] and a high [Co3+]/[Co2+] ratio are beneficial to the reaction.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
Homogenization heat treatment is a key process to remove the micro-segregation and re-dissolve the undesired phases for wrought superalloy.The oxidation behavior of the wrought superalloy during the high-temperature h...Homogenization heat treatment is a key process to remove the micro-segregation and re-dissolve the undesired phases for wrought superalloy.The oxidation behavior of the wrought superalloy during the high-temperature homogenization process,however,was rarely studied.The oxidation film evolution and growth kinetics of an as-cast superalloy Rene 65 during the homogenization were systematically studied.The oxide film consists of Cr_(2)O_(3) external oxidation layer and dendritic TiO_(2) and Al_(2)O_(3) internal oxidation layer.And the growth kinetics of the oxide film followed a parabolic law.Internal nitridation occurs during the oxidation process,and TiN is apparently formed at the tip of internal oxidation layer.The originally formed TiN can be transformed into TiO_(2) or retained with the progress of oxidation.Meanwhile,the TiN is newly formed in the deeper matrix at the new oxidation-layer tip.Thermodynamic analyses revealed that there is a competition between the oxidation and nitridation.Nitridation can occur when the partial pressure of nitrogen exceeds the threshold of nitridation and the critical partial pressure ratio of nitrogen and oxygen.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 represents the interaction of well characterized Lewis base [（Pyr）nCuX]4O2, n = 1 or 2, X = Cl, Br or I, Pyr = pyrrolidine with CO2 as a Lewis acid to produce new series of oxidative coupling and catechol...This paper represents the interaction of well characterized Lewis base [（Pyr）nCuX]4O2, n = 1 or 2, X = Cl, Br or I, Pyr = pyrrolidine with CO2 as a Lewis acid to produce new series of oxidative coupling and catechol oxidase initiators [（Pyr）nCuX]4（CO3）2. These carbonato derivatives are isolated as stable solids. They are easily soluble in aprotic solvents as CH2Cl2 or PhNO2. Cryoscopic measurements support tetranuclear core structure for all of them. Infrared spectra show differences from their oxo analogous in the carbonato domains but those differences did not distinguish between tridentate bridging carbonato and bidentate one. Rate of oxidation of 2,6-dimethylphenol （DMP） by [（Pyr）CuCl]4（CO3）2, supports coordination number six for Cu（Ⅱ） centers in [（Pyr）CuCl]4（CO3）2. In order to fulfill coordination number six, for n = 1, carbonate will act as tridentate while for n = 2, it will act as bidentate, as shown in Scheme 4. Near infrared spectra indicate a [（3 halo） Cu（Ⅱ） charge transfer] for [（Pyr）nCuX]4（CO3）2, n = 1 or 2, X = Cl or Br. Low molecular absorptivities of the maxima at 825 nm and 730 nm for [（Pyr）nCuI]4（CO3）2, n = 1 or 2 with a minimum of high molecular absorptivities at 600 nm, comparing to X= CI or Br analogous, support a step structure for [（Pyr）,Cul]4（CO3）2, as shown in Scheme 5. Cyclic voltammograms for [（Pyr）nCuX]4（CO3）2; n = 1 or 2, X = CI or Br, are irreversible in characters.展开更多
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
Due to the increasingly strict emission standards of NOx on various industries,many traditional flue gas treatment methods have been gradually improved.Except for selective catalytic reduction(SCR)and selective non-ca...Due to the increasingly strict emission standards of NOx on various industries,many traditional flue gas treatment methods have been gradually improved.Except for selective catalytic reduction(SCR)and selective non-catalytic reduction(SNCR)methods to remove NOx from flue gas,theoxidation method is paying more attention to NOx removal now because of the potential to simultaneously remove multiple pollutants from flue gas.This paper summarizes the efficiency,reaction conditions,effect factors,and reaction mechanism of NO oxidation from the aspects of liquid-phase oxidation,gas-phase oxidation,plasma technology,and catalytic oxidation.The effects of free radicals and active components of catalysts on NO oxidation and the combination of various oxidation methods are discussed in detail.The advantages and disadvantages of different oxidation methods are summarized,and the suggestions for future research on NO oxidation are put forward at the end.The review on the NO removal by oxidation methods can provide new ideas for future studies on the NO removal from flue gas.展开更多
The influence of phase components of tungsten oxide on homogeneity of ultrafine tungsten powder by conventional hydrogen reduction techniques was studied. Results show that phase components of tungsten oxide play a cr...The influence of phase components of tungsten oxide on homogeneity of ultrafine tungsten powder by conventional hydrogen reduction techniques was studied. Results show that phase components of tungsten oxide play a crucial role on homogeneity of metal tungsten powder; ultrafine and homogeneous tungsten powder can be produced from oxides which consist of only one phase. Due to the different reduction rates (or different reduction paths) of oxide which comprises different phases, the multi phase components tungsten oxide leads to a fine but in homogeneous metal tungsten powder.展开更多
Pd/Cu liquid-phase composite was utilized as the catalyst in this study to remove PH_(3) at low temperatures.The anti-heterotoxicity of catalysts in the PH_(3) catalytic oxidation purification process was carefully ex...Pd/Cu liquid-phase composite was utilized as the catalyst in this study to remove PH_(3) at low temperatures.The anti-heterotoxicity of catalysts in the PH_(3) catalytic oxidation purification process was carefully explored and pioneered.The catalytic performance,thermodynamics,kinetics,and catalytic oxidation mechanism of Pd/Cu liquid-phase catalyst catalytic oxidation of PH_(3) were thoroughly investigated.The results showed that Pd/Cu has a superior catalytic effect on the removal of PH_(3) in the gas mixture under low temperature.With CO as the carrier gas,the removal efficiency of PH_(3) could be maintained at 100%for nearly 450 min,indicating that the Pd/Cu liquid phase catalyst has good resistance to heterotoxicity.According to the thermodynamic,kinetic,and related characterization results of the PH_(3) purification process,the kinetic region of the gas–liquid reaction of PH_(3) absorption by Pd/Cu solution was an interfacial reaction.Pd was the primary catalyst and Cu was the secondary catalyst,and the adsorption of PH_(3)was a primary reaction.PH_(3) was spontaneously oxidized to H_(3)PO_(4) in the Pd/Cu catalytic system during the removal process.Pd was regenerated by O_(2) and Cu,increasing the activity and stability of the Pd/Cu catalyst in the sustain and efficient purification of PH_(3) in tail gas.展开更多
In the present study, the modified （non-Keggin-type） aqueous solutions of Mo-V-phosphoric heteropoly acids HaPzMoyVx,Oh （HPA-x＇） were applied as homogeneous catalysts for the two-stage oxidation of TMP （2,3,6-tr...In the present study, the modified （non-Keggin-type） aqueous solutions of Mo-V-phosphoric heteropoly acids HaPzMoyVx,Oh （HPA-x＇） were applied as homogeneous catalysts for the two-stage oxidation of TMP （2,3,6-trimethylphenol） by oxygen into TMQ （2,3,5-trimethyl-l,4-benzoquinone）, the latter being the key intermediate in the synthesis of vitamin E. The TMQ yield was analyzed regarding solvent type, reaction temperature, molar HPA-x ＇：TMP ratio, and the concentration of vanadium （V） in the HPA-x＇ solution. The TMQ yield was found to depend strongly on the catalyst redox potential and the rate of electron transfer. The results obtained enabled to establish the optimal reaction conditions as well as to suggest the reaction mechanism. In the target reaction, which proceeds in the two-phase system, the TMQ yield is higher than 99%. After phase separation, the catalyst is rapidly regenerated by oxygen and reused.展开更多
A new type of photocatalytic La^(3+)–Zn^(2+)–Al^(3+)–MoO_4^(2-) layered double hydroxide(LDH) material(molar ratio, La/Zn/Al = 1:7:2) was prepared by a complexing agent-assisted homogeneous precipitation technique....A new type of photocatalytic La^(3+)–Zn^(2+)–Al^(3+)–MoO_4^(2-) layered double hydroxide(LDH) material(molar ratio, La/Zn/Al = 1:7:2) was prepared by a complexing agent-assisted homogeneous precipitation technique. The structure of the prepared LDH material was systematically studied. Under UV irradiation, the desulfurization efficiency of the LDH material was 87% in 2 h. For La^(3+)–Zn^(2+)–Al^(3+)–MoO_4^(2-) LDH material, the introduction of MoO_4^(2-) increased the interlayer space for promoting the adsorption of benzothiophene(BT), and MoO_4^(2-) might provide active sites for the oxidation of BT, resulting in the high desulfurization efficiency.展开更多
Laser 3D printing based on melt growth has great potential in rapid preparation of Al_(2)O_(3)-based eutectic ce ramics.In this work,la rge-scale Al_(2)O_(3)/GdAlO_(3)/ZrO_(2)ternary eutectic ceramic rod with diameter...Laser 3D printing based on melt growth has great potential in rapid preparation of Al_(2)O_(3)-based eutectic ce ramics.In this work,la rge-scale Al_(2)O_(3)/GdAlO_(3)/ZrO_(2)ternary eutectic ceramic rod with diameter of 4-5 mm and height higher than 250 mm was additively manufactured by laser directed energy deposition.Especially,heat treatment was applied to eliminate the microstructure heterogeneity in the as-deposited eutectic ceramic,and the microstructure homogenization mechanism was studied in depth.The results indicate that colonies and banded structures completely disappear after the heat treatment,producing a homogeneous network eutectic structure.The microstructure homogenization is revealed to experience three stages of discontinuous coarsening,continuous coarsening and microstructure coalescence.Additionally,it is found that the eutectic spacing linearly increases with the heat treatment time,meaning that the coarsening behavior of the laser 3D-printed Al_(2)O_(3)/GdAlO_(3)/ZrO_(2)eutectic ceramic satisfies well with the Graham-Kraft model.展开更多
The latest progress and developments in catalysts for the oxidation of cyclohexane are reviewed. Catalytic systems for the oxidation of cyclohexane including metal supported, metal oxides, molecular sieves, metal subs...The latest progress and developments in catalysts for the oxidation of cyclohexane are reviewed. Catalytic systems for the oxidation of cyclohexane including metal supported, metal oxides, molecular sieves, metal substituted polyoxometalates, photocatalysts, orga nocatalysts, Gif systems, metal-organic catalysts and metalloporphyrins are discussed with a particular emphasis on metalloporphyrin catalytic systems. The advantages and disadvantages of these methods are summarized and analyzed. Finally, the development trends in the oxidation technology of cyclohexane are examined.展开更多
The microstructure and corrosion behavior of the as-homogenized and as-extruded Mg-xLi-3Al-2Zn-0.5Y alloys(x=4,8,12,wt.%)were studied.The results show that as the Li content increases from 4%to 12%,the matrix transfer...The microstructure and corrosion behavior of the as-homogenized and as-extruded Mg-xLi-3Al-2Zn-0.5Y alloys(x=4,8,12,wt.%)were studied.The results show that as the Li content increases from 4%to 12%,the matrix transfers from singleα-Mg phase,(α-Mg+β-Li)dual phase to singleβ-Li phase.A mixed corrosion feature of intergranular corrosion and pitting corrosion occurs in the Mg-4Li-3Al-2Zn-0.5Y and Mg-12Li-3Al-2Zn-0.5Y alloys.The former is related to the precipitated AlLi phase along the grain boundaries,and the latter is related to the high potential difference between the second phase and the matrix.The corrosion resistance of the as-extruded alloys is better than that of the as-homogenized alloys.The superior corrosion resistance of the as-extruded Mg-8Li-3Al-2Zn-0.5Y alloy with the lowest corrosion rate(P_(W)=(0.63±0.26)mm/a)is attributed to the more uniform distribution of second phases,the protectiveα-Mg phase via sacrificing theβ-Li phase and the relatively integrated oxide film.展开更多
A study on the distribution of free iron and manganese oxides was conducted in soils developed on calcareous alluvial deposits under subhumid climatic conditions, in Western Greece. Soil samples from two well drained ...A study on the distribution of free iron and manganese oxides was conducted in soils developed on calcareous alluvial deposits under subhumid climatic conditions, in Western Greece. Soil samples from two well drained soils and from two poorly drained soils, classified as Alfisols, were collected and used in this study. After certification of soil homogeneity the acid ammonium oxalate and dithionite-citrate-bicarbonate methods were used to extract free iron and manganese oxides from the samples. Iron oxides extracted by the dithionite-citrate-bicarbonate method (Fed) were significantly higher than the iron oxides extracted by the ammonium oxalate method (Feo), indicating that a considerable fraction is present in crystalline forms,independent of drainage status. A confirmation of free iron oxides and fine clay was detected. The ratios Feo/Fed and (Fed-Feo)/total Fe (Fet) could not be used to distinguish the well drained soils from the poorly drained soils. Manganese movement in a soluble form is independent of the fine clay.展开更多
The increasing demand for energy density pushes Li CoO_(2)(LCO)to work at higher voltage(≥4.5 V),which brings a series of problems including detrimental phase transition and structural instability.Various el emental ...The increasing demand for energy density pushes Li CoO_(2)(LCO)to work at higher voltage(≥4.5 V),which brings a series of problems including detrimental phase transition and structural instability.Various el emental doping has been proven an effective strategy to improve its structure stability.However,the understanding of elemental doping homogeneity effect is not enough,whether in terms of the controlla bility of doping homogeneity or its complex consequences.In this work,LCO powders with different A doping homogeneity were synthesized and tested under high voltage(≥4.5 V)in both half and full cell a room and high temperature,respectively.The results show that the Al homogeneously doped LCO showed better cycling stability and rate performance compared to the inhomogeneous LCO sample.Particularly the discharge capacity of Al homogeneously doped LCO after 500 cycles under 4.5 V in full cells could reach 160.1 mAh/g at 1.0 C with 94.1%capacity retention.Postmortem characterization demonstrates tha a better doping homogeneity favors the stability of both the bulk and interface as well as the kinetic conditions.This study provided new insights about LCO performance fading,which sheds new light on the development of high-voltage LCO products.展开更多
A copper（Ⅱ） complex with a rigid macrocyclic ligand has been synthesized and utilized as a homogeneous electrocatalyst for water oxidation in sodium phosphate buffer at pH 12,0.By using a glassy carbon electrode in...A copper（Ⅱ） complex with a rigid macrocyclic ligand has been synthesized and utilized as a homogeneous electrocatalyst for water oxidation in sodium phosphate buffer at pH 12,0.By using a glassy carbon electrode in a 3 h electrolysis,a high current density of 1.3-1.4 mA/cm2 and a turn-over number of 4 can be obtained with 1.0 mmol·L-1 of the copper catalyst at an overpotential of 750 mV.Kinetic studies revealed that the electrocatalysis with this complex is a single-site catalysis with proton-coupled electron transfers.Finally,its possible catalytic mechanism was tentatively proposed.展开更多
Intelligent chemical sensors have been extensively used in food safety and environmental assessment,while limited sensitivity and homogeneity bring about huge obstacles to their practical application.Herein,novel ioni...Intelligent chemical sensors have been extensively used in food safety and environmental assessment,while limited sensitivity and homogeneity bring about huge obstacles to their practical application.Herein,novel ionically conductive sensitive materials were elaborately designed based on metal ion decorated graphene oxide(GO)via a facile and general in-situ spin-coating strategy,where the abundant functional groups(-OH and-COOH)of GO layer could provide natural binding sites for various bivalent metal cations(such as Cu^(2+),Ni^(2+),Zn^(2+),Co^(2+),and Mg^(2+))through coordination and electrostatic inter-action.The intercalated metal cations on the layered GO nanosheets can be regarded as charge carriers and complexation with targeted gas(cadaverine,Cad),which is a typical metabolites production and food degradants.By contrast,the designed GO@Cu(Ⅱ)sensor exhibited the optimal sensing performance toward Cad molecules at room temperature,including ultra-low detection limit(ca.3 nL),excellent sensitivity,and rapid low concentration detection rate(only 16 s).Interestingly,the sensor exhibited an irreversible and specific response toward Cad,while it showed a transient and reversible response to other interfering gases,implying its outstanding selectivity.In addition,the GO@Cu(Ⅱ)sensor enabled real-time monitoring of the decay progression of cheese,and it exhibited great potential for large-scale production via its excellent homogeneity.It provides an efficient approach to tailoring intelligent chemical sensors for real-time food safety monitoring and human health warning.展开更多
基金Supported by the National Natural Science Foundation of China （20576081, 20736009） and the Ph.D. Programs Foundation of Ministry of Education of China （20070610128）.
文摘Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a φ48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH3COO)2.4H2O as catalyst.The Co2+ concentration [Co2+] was determined by extraction spectrophotometry and hereby the Co3+ concentration [Co3+] was obtained by mass balance.The results showed that [Co3+] reached the maximum at about 25-30min.[Co3+] increased with increasing Co catalyst amount at total Co concentration<150 mg.L-1 of toluene.The conversion of toluene,yield and selectivity of benzoic acid increased with the increasing [Co3+/Co2+] max.A high [Co3+] and a high [Co3+]/[Co2+] ratio are beneficial to the reaction.
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.
基金supported by the Beijing Municipal Natural Science Foundation(No.2212041)National Natural Science Foundation of China(No.51804232)supported by the Interdisciplinary Research Project for Young Teachers of USTB(Fundamental Research Funds for the Central Universities)(FRF-IDRY-20-020).
文摘Homogenization heat treatment is a key process to remove the micro-segregation and re-dissolve the undesired phases for wrought superalloy.The oxidation behavior of the wrought superalloy during the high-temperature homogenization process,however,was rarely studied.The oxidation film evolution and growth kinetics of an as-cast superalloy Rene 65 during the homogenization were systematically studied.The oxide film consists of Cr_(2)O_(3) external oxidation layer and dendritic TiO_(2) and Al_(2)O_(3) internal oxidation layer.And the growth kinetics of the oxide film followed a parabolic law.Internal nitridation occurs during the oxidation process,and TiN is apparently formed at the tip of internal oxidation layer.The originally formed TiN can be transformed into TiO_(2) or retained with the progress of oxidation.Meanwhile,the TiN is newly formed in the deeper matrix at the new oxidation-layer tip.Thermodynamic analyses revealed that there is a competition between the oxidation and nitridation.Nitridation can occur when the partial pressure of nitrogen exceeds the threshold of nitridation and the critical partial pressure ratio of nitrogen and oxygen.
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 represents the interaction of well characterized Lewis base [（Pyr）nCuX]4O2, n = 1 or 2, X = Cl, Br or I, Pyr = pyrrolidine with CO2 as a Lewis acid to produce new series of oxidative coupling and catechol oxidase initiators [（Pyr）nCuX]4（CO3）2. These carbonato derivatives are isolated as stable solids. They are easily soluble in aprotic solvents as CH2Cl2 or PhNO2. Cryoscopic measurements support tetranuclear core structure for all of them. Infrared spectra show differences from their oxo analogous in the carbonato domains but those differences did not distinguish between tridentate bridging carbonato and bidentate one. Rate of oxidation of 2,6-dimethylphenol （DMP） by [（Pyr）CuCl]4（CO3）2, supports coordination number six for Cu（Ⅱ） centers in [（Pyr）CuCl]4（CO3）2. In order to fulfill coordination number six, for n = 1, carbonate will act as tridentate while for n = 2, it will act as bidentate, as shown in Scheme 4. Near infrared spectra indicate a [（3 halo） Cu（Ⅱ） charge transfer] for [（Pyr）nCuX]4（CO3）2, n = 1 or 2, X = Cl or Br. Low molecular absorptivities of the maxima at 825 nm and 730 nm for [（Pyr）nCuI]4（CO3）2, n = 1 or 2 with a minimum of high molecular absorptivities at 600 nm, comparing to X= CI or Br analogous, support a step structure for [（Pyr）,Cul]4（CO3）2, as shown in Scheme 5. Cyclic voltammograms for [（Pyr）nCuX]4（CO3）2; n = 1 or 2, X = CI or Br, are irreversible in characters.
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 National Key Research and Development Program of China(No.2018YFB0605101)the Key Project Natural Science Foundation of Tianjin(No.18JCZDJC39800)+4 种基金the Key R&D projects in Hebei Province(No.20373701D)the National Natural Science Foundation of China(No.51808181)the Science and Technology Key Project of Tianjin(Nos.18ZXSZSF00040,18KPXMSF00080,18PTZWHZ00010)Department of Education of Hebei Province(No.BJ2017032)Joint Doctoral Training Foundation of HEBUT(No.2017HW0002)。
文摘Due to the increasingly strict emission standards of NOx on various industries,many traditional flue gas treatment methods have been gradually improved.Except for selective catalytic reduction(SCR)and selective non-catalytic reduction(SNCR)methods to remove NOx from flue gas,theoxidation method is paying more attention to NOx removal now because of the potential to simultaneously remove multiple pollutants from flue gas.This paper summarizes the efficiency,reaction conditions,effect factors,and reaction mechanism of NO oxidation from the aspects of liquid-phase oxidation,gas-phase oxidation,plasma technology,and catalytic oxidation.The effects of free radicals and active components of catalysts on NO oxidation and the combination of various oxidation methods are discussed in detail.The advantages and disadvantages of different oxidation methods are summarized,and the suggestions for future research on NO oxidation are put forward at the end.The review on the NO removal by oxidation methods can provide new ideas for future studies on the NO removal from flue gas.
文摘The influence of phase components of tungsten oxide on homogeneity of ultrafine tungsten powder by conventional hydrogen reduction techniques was studied. Results show that phase components of tungsten oxide play a crucial role on homogeneity of metal tungsten powder; ultrafine and homogeneous tungsten powder can be produced from oxides which consist of only one phase. Due to the different reduction rates (or different reduction paths) of oxide which comprises different phases, the multi phase components tungsten oxide leads to a fine but in homogeneous metal tungsten powder.
基金supported by the National Key Research and Development Plan (2018YFC1900203)The National Science Fund for Distinguished Young Scholars (52000094)The National Natural Science Foundation of China (51968033)。
文摘Pd/Cu liquid-phase composite was utilized as the catalyst in this study to remove PH_(3) at low temperatures.The anti-heterotoxicity of catalysts in the PH_(3) catalytic oxidation purification process was carefully explored and pioneered.The catalytic performance,thermodynamics,kinetics,and catalytic oxidation mechanism of Pd/Cu liquid-phase catalyst catalytic oxidation of PH_(3) were thoroughly investigated.The results showed that Pd/Cu has a superior catalytic effect on the removal of PH_(3) in the gas mixture under low temperature.With CO as the carrier gas,the removal efficiency of PH_(3) could be maintained at 100%for nearly 450 min,indicating that the Pd/Cu liquid phase catalyst has good resistance to heterotoxicity.According to the thermodynamic,kinetic,and related characterization results of the PH_(3) purification process,the kinetic region of the gas–liquid reaction of PH_(3) absorption by Pd/Cu solution was an interfacial reaction.Pd was the primary catalyst and Cu was the secondary catalyst,and the adsorption of PH_(3)was a primary reaction.PH_(3) was spontaneously oxidized to H_(3)PO_(4) in the Pd/Cu catalytic system during the removal process.Pd was regenerated by O_(2) and Cu,increasing the activity and stability of the Pd/Cu catalyst in the sustain and efficient purification of PH_(3) in tail gas.
文摘In the present study, the modified （non-Keggin-type） aqueous solutions of Mo-V-phosphoric heteropoly acids HaPzMoyVx,Oh （HPA-x＇） were applied as homogeneous catalysts for the two-stage oxidation of TMP （2,3,6-trimethylphenol） by oxygen into TMQ （2,3,5-trimethyl-l,4-benzoquinone）, the latter being the key intermediate in the synthesis of vitamin E. The TMQ yield was analyzed regarding solvent type, reaction temperature, molar HPA-x ＇：TMP ratio, and the concentration of vanadium （V） in the HPA-x＇ solution. The TMQ yield was found to depend strongly on the catalyst redox potential and the rate of electron transfer. The results obtained enabled to establish the optimal reaction conditions as well as to suggest the reaction mechanism. In the target reaction, which proceeds in the two-phase system, the TMQ yield is higher than 99%. After phase separation, the catalyst is rapidly regenerated by oxygen and reused.
文摘A new type of photocatalytic La^(3+)–Zn^(2+)–Al^(3+)–MoO_4^(2-) layered double hydroxide(LDH) material(molar ratio, La/Zn/Al = 1:7:2) was prepared by a complexing agent-assisted homogeneous precipitation technique. The structure of the prepared LDH material was systematically studied. Under UV irradiation, the desulfurization efficiency of the LDH material was 87% in 2 h. For La^(3+)–Zn^(2+)–Al^(3+)–MoO_4^(2-) LDH material, the introduction of MoO_4^(2-) increased the interlayer space for promoting the adsorption of benzothiophene(BT), and MoO_4^(2-) might provide active sites for the oxidation of BT, resulting in the high desulfurization efficiency.
基金financially supported by the National Key R&D Program of China(Nos.2018YFB1106600 and 2017YFB1103500)Science,Technology and Innovation Commission of Shenzhen Municipality(No.JCYJ20180306171121424)+4 种基金National Natural Science Foundation of China(Nos.51822405,51472200)Aeronautics Power Foundation(No.6141B09050337)Key R&D Program of Shaan Xi Province(No.2018ZDCXL-GY-09-04)Joint Research Funds of the Department of Science&Technology of Shaanxi Province and NPU(No.2020GXLH-Z-024)Research Fund of the State Key Laboratory of Solidification Processing(NPU)(No.2019QZ-02)。
文摘Laser 3D printing based on melt growth has great potential in rapid preparation of Al_(2)O_(3)-based eutectic ce ramics.In this work,la rge-scale Al_(2)O_(3)/GdAlO_(3)/ZrO_(2)ternary eutectic ceramic rod with diameter of 4-5 mm and height higher than 250 mm was additively manufactured by laser directed energy deposition.Especially,heat treatment was applied to eliminate the microstructure heterogeneity in the as-deposited eutectic ceramic,and the microstructure homogenization mechanism was studied in depth.The results indicate that colonies and banded structures completely disappear after the heat treatment,producing a homogeneous network eutectic structure.The microstructure homogenization is revealed to experience three stages of discontinuous coarsening,continuous coarsening and microstructure coalescence.Additionally,it is found that the eutectic spacing linearly increases with the heat treatment time,meaning that the coarsening behavior of the laser 3D-printed Al_(2)O_(3)/GdAlO_(3)/ZrO_(2)eutectic ceramic satisfies well with the Graham-Kraft model.
文摘The latest progress and developments in catalysts for the oxidation of cyclohexane are reviewed. Catalytic systems for the oxidation of cyclohexane including metal supported, metal oxides, molecular sieves, metal substituted polyoxometalates, photocatalysts, orga nocatalysts, Gif systems, metal-organic catalysts and metalloporphyrins are discussed with a particular emphasis on metalloporphyrin catalytic systems. The advantages and disadvantages of these methods are summarized and analyzed. Finally, the development trends in the oxidation technology of cyclohexane are examined.
基金financially supported by the National Natural Science Foundation of China(Nos.51771115,51775334,51821001,U2037601)Open Fund of State Key Laboratory of Advanced Forming Technology and Equipment(No.SKL2020005)。
文摘The microstructure and corrosion behavior of the as-homogenized and as-extruded Mg-xLi-3Al-2Zn-0.5Y alloys(x=4,8,12,wt.%)were studied.The results show that as the Li content increases from 4%to 12%,the matrix transfers from singleα-Mg phase,(α-Mg+β-Li)dual phase to singleβ-Li phase.A mixed corrosion feature of intergranular corrosion and pitting corrosion occurs in the Mg-4Li-3Al-2Zn-0.5Y and Mg-12Li-3Al-2Zn-0.5Y alloys.The former is related to the precipitated AlLi phase along the grain boundaries,and the latter is related to the high potential difference between the second phase and the matrix.The corrosion resistance of the as-extruded alloys is better than that of the as-homogenized alloys.The superior corrosion resistance of the as-extruded Mg-8Li-3Al-2Zn-0.5Y alloy with the lowest corrosion rate(P_(W)=(0.63±0.26)mm/a)is attributed to the more uniform distribution of second phases,the protectiveα-Mg phase via sacrificing theβ-Li phase and the relatively integrated oxide film.
文摘A study on the distribution of free iron and manganese oxides was conducted in soils developed on calcareous alluvial deposits under subhumid climatic conditions, in Western Greece. Soil samples from two well drained soils and from two poorly drained soils, classified as Alfisols, were collected and used in this study. After certification of soil homogeneity the acid ammonium oxalate and dithionite-citrate-bicarbonate methods were used to extract free iron and manganese oxides from the samples. Iron oxides extracted by the dithionite-citrate-bicarbonate method (Fed) were significantly higher than the iron oxides extracted by the ammonium oxalate method (Feo), indicating that a considerable fraction is present in crystalline forms,independent of drainage status. A confirmation of free iron oxides and fine clay was detected. The ratios Feo/Fed and (Fed-Feo)/total Fe (Fet) could not be used to distinguish the well drained soils from the poorly drained soils. Manganese movement in a soluble form is independent of the fine clay.
基金supported by the National Natural Science Foundation of China(No.52122407)the Science and Technology Innovation Program of Hunan Province(No.2022RC3048)the Key Research and Development Program of Yunnan Province(No.202103AA080019)。
文摘The increasing demand for energy density pushes Li CoO_(2)(LCO)to work at higher voltage(≥4.5 V),which brings a series of problems including detrimental phase transition and structural instability.Various el emental doping has been proven an effective strategy to improve its structure stability.However,the understanding of elemental doping homogeneity effect is not enough,whether in terms of the controlla bility of doping homogeneity or its complex consequences.In this work,LCO powders with different A doping homogeneity were synthesized and tested under high voltage(≥4.5 V)in both half and full cell a room and high temperature,respectively.The results show that the Al homogeneously doped LCO showed better cycling stability and rate performance compared to the inhomogeneous LCO sample.Particularly the discharge capacity of Al homogeneously doped LCO after 500 cycles under 4.5 V in full cells could reach 160.1 mAh/g at 1.0 C with 94.1%capacity retention.Postmortem characterization demonstrates tha a better doping homogeneity favors the stability of both the bulk and interface as well as the kinetic conditions.This study provided new insights about LCO performance fading,which sheds new light on the development of high-voltage LCO products.
文摘A copper（Ⅱ） complex with a rigid macrocyclic ligand has been synthesized and utilized as a homogeneous electrocatalyst for water oxidation in sodium phosphate buffer at pH 12,0.By using a glassy carbon electrode in a 3 h electrolysis,a high current density of 1.3-1.4 mA/cm2 and a turn-over number of 4 can be obtained with 1.0 mmol·L-1 of the copper catalyst at an overpotential of 750 mV.Kinetic studies revealed that the electrocatalysis with this complex is a single-site catalysis with proton-coupled electron transfers.Finally,its possible catalytic mechanism was tentatively proposed.
基金supported by the National Natural Science Foundation of China(Nos.62074111,22105043)the Science&Technology Foundation of Shanghai(Nos.19JC1412402,20JC1415600)+2 种基金Shanghai Municipal Science and Technology Major Project(No.2021SHZDZX0100)Shanghai Municipal Commission of Science and Technology Project(No.19511132101)the support of the Fundamental Research Funds for the Central Universities
文摘Intelligent chemical sensors have been extensively used in food safety and environmental assessment,while limited sensitivity and homogeneity bring about huge obstacles to their practical application.Herein,novel ionically conductive sensitive materials were elaborately designed based on metal ion decorated graphene oxide(GO)via a facile and general in-situ spin-coating strategy,where the abundant functional groups(-OH and-COOH)of GO layer could provide natural binding sites for various bivalent metal cations(such as Cu^(2+),Ni^(2+),Zn^(2+),Co^(2+),and Mg^(2+))through coordination and electrostatic inter-action.The intercalated metal cations on the layered GO nanosheets can be regarded as charge carriers and complexation with targeted gas(cadaverine,Cad),which is a typical metabolites production and food degradants.By contrast,the designed GO@Cu(Ⅱ)sensor exhibited the optimal sensing performance toward Cad molecules at room temperature,including ultra-low detection limit(ca.3 nL),excellent sensitivity,and rapid low concentration detection rate(only 16 s).Interestingly,the sensor exhibited an irreversible and specific response toward Cad,while it showed a transient and reversible response to other interfering gases,implying its outstanding selectivity.In addition,the GO@Cu(Ⅱ)sensor enabled real-time monitoring of the decay progression of cheese,and it exhibited great potential for large-scale production via its excellent homogeneity.It provides an efficient approach to tailoring intelligent chemical sensors for real-time food safety monitoring and human health warning.
