Liquid phase catalytic hydroxylation of phenol by Fe-containing metal-organic framework, Fe-BTC (BTC = 1,3,5-benzenetricarboxylate) using 30% H2O2 as an oxidant and H2O as solvent showed good activity and stability un...Liquid phase catalytic hydroxylation of phenol by Fe-containing metal-organic framework, Fe-BTC (BTC = 1,3,5-benzenetricarboxylate) using 30% H2O2 as an oxidant and H2O as solvent showed good activity and stability under mild reaction conditions. Phenol reacts with hydrogen peroxide over Fe-BTC to produce two main products, viz., catechol and hydroquinone. The effect of temperature, time, substrate/hydrogen peroxide mole ratio and amount of catalyst on catalytic performance were studied. The catalyst could be reused four times without losing significant loss of catalytic performance. The crystallinity and structure of catalyst were unchanged during the catalysis reaction, as confirmed by comparison of XRD and SEM of the fresh and reused catalyst. A reaction mechanism is proposed based on the experimental results.展开更多
The paper presents results of phenol oxidized under the conditions of high temperature created during collapse of cavitation bubbles.The degradation efficiency has been greatly improved by using cavitation water jets ...The paper presents results of phenol oxidized under the conditions of high temperature created during collapse of cavitation bubbles.The degradation efficiency has been greatly improved by using cavitation water jets combined with H2O2 as demonstrated in laboratory tests.Various factors affecting phenol removal ratio were ex-amined and the degradation mechanism was revealed by high performance liquid chromatography(HPLC).The re-sults showed that 99.85% of phenol was mineralized when phenol concentration was 100 mg·L-1 with pH value of 3.0,H2O2 concentration of 300 mg·L-1,confining pressure of 0.5 MPa,and pumping pressure of 20 MPa.The in-termediate products after phenol oxidation were composed of catechol,hydroquinone and p-benzoquinone.Finally,phenol was degraded into maleic acid and acetic acid.Furthermore,a dynamic model of phenol oxidation via cavi-tation water jets combined with H2O2 has been developed.展开更多
In this study,two series of cerium zirconium mixed oxides CeZrLaPrOwere prepared under traditional co-precipitation and oxidation co-precipitation methods respectively. The physicochemical properties of the samples we...In this study,two series of cerium zirconium mixed oxides CeZrLaPrOwere prepared under traditional co-precipitation and oxidation co-precipitation methods respectively. The physicochemical properties of the samples were compared under these two methods and assessed by XRD,Raman,BET,TEM,HTPR,OSC,XPS and catalysts measurements. The formation of homogeneity phase structure can be facilitated by changing the precipitating properties of Ce3+ under oxidation coprecipitation method, which is helpful to enhance the homogeneity of Ce and Zr at atomic level.What’s more, it is conducive to remove impurities Na~+ and Cl~-by oxidation co-precipitation with hydrogen peroxide. The catalysts activities are related to both the redox properties and the textural properties of mixed oxides. The Pd-only TWCs supported on the CZLP-H-F exhibits better catalytic performance and thermal stability with wider air/fuel ratio operation window, lower light-off and full conversion temperatures of CHand NO. The homogeneity of phase structure for cerium zirconium mixed oxide can be predicted and deduced from detecting the atomic distribution uniformity of its precursor. So this work not only provides insights into the mechanisms for phase segregation of cerium zirconium mixed oxide, but also provides a guidance to improve homogeneity of cerium zirconium mixed oxide by adding additives.展开更多
Mixed oxides Ln2CuO4±λ(Ln=La,Pr,Nd,Sm,Gd) with K2NiF4 structure were prepared Their crystal structures were studied with XRD and IR spectra.Meanwhile,the average valence of Cu ions and non stoichiometric oxygen ...Mixed oxides Ln2CuO4±λ(Ln=La,Pr,Nd,Sm,Gd) with K2NiF4 structure were prepared Their crystal structures were studied with XRD and IR spectra.Meanwhile,the average valence of Cu ions and non stoichiometric oxygen (λ) were determined through chemical analyses.Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated.Results show that the catalysis of these mixed oxides has close relation with their structures and composition.Substitution of A site atom in Ln2CuO4λ has a great influence on then eatalysis in the phenol hydroxylation.展开更多
Two groups of mixed oxides La2-xThxCuO4±λ(0.0≤x≤0.4)and La2-xSrxCuO4±λ(0.0≤x≤1.0) were prepared.Their crystal structures were studied with XRD and IR spectra,etc.Meanwhile,the average valence of Cu ion...Two groups of mixed oxides La2-xThxCuO4±λ(0.0≤x≤0.4)and La2-xSrxCuO4±λ(0.0≤x≤1.0) were prepared.Their crystal structures were studied with XRD and IR spectra,etc.Meanwhile,the average valence of Cu ions and nonstoichiometric oxygen (λ) was measured through chemical analyses.Catalysis of the above-mentioned mixed oxides was investigated in phenol hydroxylation,good results were obtained for some mixed oxides,and found that the catalysis of these mixed oxides have close relation with their defect structure and composition.A radical substitution mechanism was also proposed for this catalytic reaction.展开更多
Superconductor mixed oxides were often used as catalysts at higher temperature in gas phase oxidations, and considered not suitable for lower temperature reactions in the liquid-solid phase; here the catalysis of YBa2...Superconductor mixed oxides were often used as catalysts at higher temperature in gas phase oxidations, and considered not suitable for lower temperature reactions in the liquid-solid phase; here the catalysis of YBa2Cu3O7+/-x and Y2BaCuO5+/-x in the phenol hydroxylation at lower temperature with H2O2 as oxygen donor was studied, and found that the superconductor YBa2Cu3O7+/-x, has no catalytic activity for phenol hydroxylation, but Y2BaCuO5+/-x does, even has better catalytic activity and stability than most previously reported ones. With the studies of catalysis of other simple metal oxides and perovskite-like mixed oxides, a radical substitution mechanism is proposed and the experimental facts are explained clearly, and draw a conclusion that the perovskite-like mixed oxides with (AO)(ABO(3)) and (AO)2(ABO(3)) structure have better catalytic activity than the simple perovskite oxides with (ABO(3))(3) structure alone, and (AO) structure unit is the key for the mixed oxides to have the phenol hydroxylation activity. No pollution of this process is very important for its further industrial application.展开更多
In this study,Pd-Mg(Al)-LDH/γ-Al2O3 and Pd-Mg(Al)Zr-LDH/γ-Al2O3 precursors were synthesized by impregnating Na2PdCl4 on Mg(Al)-LDH/γ-Al2O3 and Mg(Al)Zr-LDH/γ-Al2O3,and then the precursors were calcinated and reduc...In this study,Pd-Mg(Al)-LDH/γ-Al2O3 and Pd-Mg(Al)Zr-LDH/γ-Al2O3 precursors were synthesized by impregnating Na2PdCl4 on Mg(Al)-LDH/γ-Al2O3 and Mg(Al)Zr-LDH/γ-Al2O3,and then the precursors were calcinated and reduced to obtain Pd-Mg(Al)-MMO/γ-Al2O3 and Pd-Mg(Al)Zr-MMO/γ-Al2O3 catalysts.Compared with Pd/γ-Al2O3 catalyst,the hydrogenation efficiency of Pd-Mg(Al)-MMO/γ-Al2O3 and Pd-Mg(Al)Zr-MMO/γ-Al2O3 increased by 15.7%and 24.0%,respectively.Moreover,the stability of Pd-Mg(Al)Zr-MMO/γ-Al2O3 catalyst was also higher than that of Pd/γ-Al2O3.After four runs,the hydrogenation efficiency of Pd/γ-Al2O3 decreased from 12.1 to 10.0 g/L,while that of Pd-Mg(Al)Zr-MMO/γ-Al2O3 decreased from 15.0 to 14.3 g/L.The active aquinones selectivities of all catalysts were almost 99%.The structures of the catalysts were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),N2 adsorption–desorption,inductively coupled plasma-atomic emission spectrometry(ICP-AES),CO chemisorption analysis,transmission electron microscopy(TEM),temperature-programmed reduction with hydrogen(H2-TPR),and X-ray photoelectron spectroscopy(XPS).The results indicate that the improved catalytic performance is attributed to the stronger interaction between Pd and Mg(Al)Zr-MMO/γ-Al2O3,smaller Pd particle size and higher Pd dispersion.This work develops an effective method to synthesize highly dispersed Pd nanoparticles based on the layered double hydroxides(LDHs)precursor.展开更多
We report a study of the roles of gadolinium(lll)(Gd3+)dopants in influencing the catalytic activity of gadolinium-doped ceria nanoparticles towards the pro-oxidation of hydrogen peroxide to hydroxyl radicals.These do...We report a study of the roles of gadolinium(lll)(Gd3+)dopants in influencing the catalytic activity of gadolinium-doped ceria nanoparticles towards the pro-oxidation of hydrogen peroxide to hydroxyl radicals.These doped ceria nanoparticles with dopant concentrations of 0.6 wt.%,3 wt.%,and 6 wt.%Gd^3+were synthesized using an ozone-mediated method for tuning their catalytic activities.The Gd dopants were found to foster an increase in the percentage of Ce^3+ions in the doped ceria nanoparticles.Our reaction kinetic study revealed that the relationship between the overall reaction rates and the Gd dopant concentrations in our doped materials followed a volcano-like trend.In contrast,the apparent activation energy values of these Gd-doped ceria nanoparticles were found to be positively associated with the concentrations of Gd dopants.The overall catalytic activity trend was attributed to the interplay between the promotion and degradation effects of the Gd dopants on the properties of doped ceria nanoparticles.展开更多
A terylene membrane which kept pH〉12 in cathode compartment was used to construct a divided cell with a carbon/polytetrafluoroethylene(C/PTFE) O2-fed cathode. The concentrations of hydrogen peroxide (H2O2) and hy...A terylene membrane which kept pH〉12 in cathode compartment was used to construct a divided cell with a carbon/polytetrafluoroethylene(C/PTFE) O2-fed cathode. The concentrations of hydrogen peroxide (H2O2) and hydroxyl radical (HO^-)in the catholyte were 8.3 mg/L and 2.15 μmol/L, respectivel.y, which were determined by permanganate titration, electron spin resonance (ESR) spectrum and the fluorescence spectra. ;The efficiency of the removal of phenol achieved 100% as a result of these two kinds of stronger oxidizer.展开更多
Phenol in waste water threatens human health and is difficultly to be decomposed by nature.Efficient degradation of high-loaded phenol in water under mild condition is still a great challenge.Herein,ionic liquids with...Phenol in waste water threatens human health and is difficultly to be decomposed by nature.Efficient degradation of high-loaded phenol in water under mild condition is still a great challenge.Herein,ionic liquids with tungstate anion were designed and prepared.It was found that dodecyltrimethylammonium tungstate could catalyzed degradation of phenol into gases and water thoroughly at 323 k in 8 h.Tungstate anion revealed good catalytic oxidative activity and long carbon chain group connecting with cation of ionic liquids enriched phenol around catalysts,which induced the complete degradation of phenol at mild conditions.Increasing the amounts of hydrogen peroxide benefited to the total degradation of phenol.In addition,the ionic liquid could be reused for its excellent thermal stability.Our work provided a different strategy to treat waste water containing phenol efficiently.展开更多
A novel catalyst, MgFe 2O 4, for hydroxylation of phenol with hydrogen peroxide was synthesized via coprecipitation method from an aqueous solution containing Fe(NO 3) 3·9H 2O and Mg(NO 3) 2·6H 2O with ammon...A novel catalyst, MgFe 2O 4, for hydroxylation of phenol with hydrogen peroxide was synthesized via coprecipitation method from an aqueous solution containing Fe(NO 3) 3·9H 2O and Mg(NO 3) 2·6H 2O with ammonia. The X ray diffraction peaks of the catalyst show that the as prepared sample has engendered MgFe 2O 4 crystal with spinel structure, which is also confirmed by its IR spectrum. In the hydroxylation of phenol with hydrogen peroxide, MgFe 2O 4 catalyst exhibited high activity after a short induction period. In particular, the addition of a little amount of acetic acid in the reaction liquid can effectively shorten the induction period. Under the same reaction conditions, the diphenol selectivity over MgFe 2O 4 is higher than that over TS 1, furthermore, the reaction time is shortened greatly. The experimental phenomena can be explained by the free radical mechanism.展开更多
文摘Liquid phase catalytic hydroxylation of phenol by Fe-containing metal-organic framework, Fe-BTC (BTC = 1,3,5-benzenetricarboxylate) using 30% H2O2 as an oxidant and H2O as solvent showed good activity and stability under mild reaction conditions. Phenol reacts with hydrogen peroxide over Fe-BTC to produce two main products, viz., catechol and hydroquinone. The effect of temperature, time, substrate/hydrogen peroxide mole ratio and amount of catalyst on catalytic performance were studied. The catalyst could be reused four times without losing significant loss of catalytic performance. The crystallinity and structure of catalyst were unchanged during the catalysis reaction, as confirmed by comparison of XRD and SEM of the fresh and reused catalyst. A reaction mechanism is proposed based on the experimental results.
基金Supported by the National Natural Science Foundation of China (50921063,51104191)the Natural Science Foundationof Chongqing (2009BA6047)
文摘The paper presents results of phenol oxidized under the conditions of high temperature created during collapse of cavitation bubbles.The degradation efficiency has been greatly improved by using cavitation water jets combined with H2O2 as demonstrated in laboratory tests.Various factors affecting phenol removal ratio were ex-amined and the degradation mechanism was revealed by high performance liquid chromatography(HPLC).The re-sults showed that 99.85% of phenol was mineralized when phenol concentration was 100 mg·L-1 with pH value of 3.0,H2O2 concentration of 300 mg·L-1,confining pressure of 0.5 MPa,and pumping pressure of 20 MPa.The in-termediate products after phenol oxidation were composed of catechol,hydroquinone and p-benzoquinone.Finally,phenol was degraded into maleic acid and acetic acid.Furthermore,a dynamic model of phenol oxidation via cavi-tation water jets combined with H2O2 has been developed.
基金the financial supports from Grirem Advanced Materials Co.,Ltd.
文摘In this study,two series of cerium zirconium mixed oxides CeZrLaPrOwere prepared under traditional co-precipitation and oxidation co-precipitation methods respectively. The physicochemical properties of the samples were compared under these two methods and assessed by XRD,Raman,BET,TEM,HTPR,OSC,XPS and catalysts measurements. The formation of homogeneity phase structure can be facilitated by changing the precipitating properties of Ce3+ under oxidation coprecipitation method, which is helpful to enhance the homogeneity of Ce and Zr at atomic level.What’s more, it is conducive to remove impurities Na~+ and Cl~-by oxidation co-precipitation with hydrogen peroxide. The catalysts activities are related to both the redox properties and the textural properties of mixed oxides. The Pd-only TWCs supported on the CZLP-H-F exhibits better catalytic performance and thermal stability with wider air/fuel ratio operation window, lower light-off and full conversion temperatures of CHand NO. The homogeneity of phase structure for cerium zirconium mixed oxide can be predicted and deduced from detecting the atomic distribution uniformity of its precursor. So this work not only provides insights into the mechanisms for phase segregation of cerium zirconium mixed oxide, but also provides a guidance to improve homogeneity of cerium zirconium mixed oxide by adding additives.
基金Project supported by the National Natural Science Foundation of China
文摘Mixed oxides Ln2CuO4±λ(Ln=La,Pr,Nd,Sm,Gd) with K2NiF4 structure were prepared Their crystal structures were studied with XRD and IR spectra.Meanwhile,the average valence of Cu ions and non stoichiometric oxygen (λ) were determined through chemical analyses.Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated.Results show that the catalysis of these mixed oxides has close relation with their structures and composition.Substitution of A site atom in Ln2CuO4λ has a great influence on then eatalysis in the phenol hydroxylation.
文摘Two groups of mixed oxides La2-xThxCuO4±λ(0.0≤x≤0.4)and La2-xSrxCuO4±λ(0.0≤x≤1.0) were prepared.Their crystal structures were studied with XRD and IR spectra,etc.Meanwhile,the average valence of Cu ions and nonstoichiometric oxygen (λ) was measured through chemical analyses.Catalysis of the above-mentioned mixed oxides was investigated in phenol hydroxylation,good results were obtained for some mixed oxides,and found that the catalysis of these mixed oxides have close relation with their defect structure and composition.A radical substitution mechanism was also proposed for this catalytic reaction.
文摘Superconductor mixed oxides were often used as catalysts at higher temperature in gas phase oxidations, and considered not suitable for lower temperature reactions in the liquid-solid phase; here the catalysis of YBa2Cu3O7+/-x and Y2BaCuO5+/-x in the phenol hydroxylation at lower temperature with H2O2 as oxygen donor was studied, and found that the superconductor YBa2Cu3O7+/-x, has no catalytic activity for phenol hydroxylation, but Y2BaCuO5+/-x does, even has better catalytic activity and stability than most previously reported ones. With the studies of catalysis of other simple metal oxides and perovskite-like mixed oxides, a radical substitution mechanism is proposed and the experimental facts are explained clearly, and draw a conclusion that the perovskite-like mixed oxides with (AO)(ABO(3)) and (AO)2(ABO(3)) structure have better catalytic activity than the simple perovskite oxides with (ABO(3))(3) structure alone, and (AO) structure unit is the key for the mixed oxides to have the phenol hydroxylation activity. No pollution of this process is very important for its further industrial application.
基金supported by the National Natural Science Foundation of China (Nos. 21276179, 21576205)the Program for Changjiang Scholars, Innovative Research Team in University (IRT_15R46)
文摘In this study,Pd-Mg(Al)-LDH/γ-Al2O3 and Pd-Mg(Al)Zr-LDH/γ-Al2O3 precursors were synthesized by impregnating Na2PdCl4 on Mg(Al)-LDH/γ-Al2O3 and Mg(Al)Zr-LDH/γ-Al2O3,and then the precursors were calcinated and reduced to obtain Pd-Mg(Al)-MMO/γ-Al2O3 and Pd-Mg(Al)Zr-MMO/γ-Al2O3 catalysts.Compared with Pd/γ-Al2O3 catalyst,the hydrogenation efficiency of Pd-Mg(Al)-MMO/γ-Al2O3 and Pd-Mg(Al)Zr-MMO/γ-Al2O3 increased by 15.7%and 24.0%,respectively.Moreover,the stability of Pd-Mg(Al)Zr-MMO/γ-Al2O3 catalyst was also higher than that of Pd/γ-Al2O3.After four runs,the hydrogenation efficiency of Pd/γ-Al2O3 decreased from 12.1 to 10.0 g/L,while that of Pd-Mg(Al)Zr-MMO/γ-Al2O3 decreased from 15.0 to 14.3 g/L.The active aquinones selectivities of all catalysts were almost 99%.The structures of the catalysts were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),N2 adsorption–desorption,inductively coupled plasma-atomic emission spectrometry(ICP-AES),CO chemisorption analysis,transmission electron microscopy(TEM),temperature-programmed reduction with hydrogen(H2-TPR),and X-ray photoelectron spectroscopy(XPS).The results indicate that the improved catalytic performance is attributed to the stronger interaction between Pd and Mg(Al)Zr-MMO/γ-Al2O3,smaller Pd particle size and higher Pd dispersion.This work develops an effective method to synthesize highly dispersed Pd nanoparticles based on the layered double hydroxides(LDHs)precursor.
基金C.L.C.,A.B.,and T.J.F.gratefully acknowledge the financial support from the National Science Foundation(No.CHE-1362916)Y.G.and D.W.Z.were supported by the CASShanghai Science Research Center(No.CAS-SSRC-YJ-2015-01)the National Natural Science Foundation of China(Nos.11574340 and 21773287).
文摘We report a study of the roles of gadolinium(lll)(Gd3+)dopants in influencing the catalytic activity of gadolinium-doped ceria nanoparticles towards the pro-oxidation of hydrogen peroxide to hydroxyl radicals.These doped ceria nanoparticles with dopant concentrations of 0.6 wt.%,3 wt.%,and 6 wt.%Gd^3+were synthesized using an ozone-mediated method for tuning their catalytic activities.The Gd dopants were found to foster an increase in the percentage of Ce^3+ions in the doped ceria nanoparticles.Our reaction kinetic study revealed that the relationship between the overall reaction rates and the Gd dopant concentrations in our doped materials followed a volcano-like trend.In contrast,the apparent activation energy values of these Gd-doped ceria nanoparticles were found to be positively associated with the concentrations of Gd dopants.The overall catalytic activity trend was attributed to the interplay between the promotion and degradation effects of the Gd dopants on the properties of doped ceria nanoparticles.
文摘A terylene membrane which kept pH〉12 in cathode compartment was used to construct a divided cell with a carbon/polytetrafluoroethylene(C/PTFE) O2-fed cathode. The concentrations of hydrogen peroxide (H2O2) and hydroxyl radical (HO^-)in the catholyte were 8.3 mg/L and 2.15 μmol/L, respectivel.y, which were determined by permanganate titration, electron spin resonance (ESR) spectrum and the fluorescence spectra. ;The efficiency of the removal of phenol achieved 100% as a result of these two kinds of stronger oxidizer.
基金financially supported by the National Natural Science Foundation of China(21875265,22293015,22121002)。
文摘Phenol in waste water threatens human health and is difficultly to be decomposed by nature.Efficient degradation of high-loaded phenol in water under mild condition is still a great challenge.Herein,ionic liquids with tungstate anion were designed and prepared.It was found that dodecyltrimethylammonium tungstate could catalyzed degradation of phenol into gases and water thoroughly at 323 k in 8 h.Tungstate anion revealed good catalytic oxidative activity and long carbon chain group connecting with cation of ionic liquids enriched phenol around catalysts,which induced the complete degradation of phenol at mild conditions.Increasing the amounts of hydrogen peroxide benefited to the total degradation of phenol.In addition,the ionic liquid could be reused for its excellent thermal stability.Our work provided a different strategy to treat waste water containing phenol efficiently.
文摘A novel catalyst, MgFe 2O 4, for hydroxylation of phenol with hydrogen peroxide was synthesized via coprecipitation method from an aqueous solution containing Fe(NO 3) 3·9H 2O and Mg(NO 3) 2·6H 2O with ammonia. The X ray diffraction peaks of the catalyst show that the as prepared sample has engendered MgFe 2O 4 crystal with spinel structure, which is also confirmed by its IR spectrum. In the hydroxylation of phenol with hydrogen peroxide, MgFe 2O 4 catalyst exhibited high activity after a short induction period. In particular, the addition of a little amount of acetic acid in the reaction liquid can effectively shorten the induction period. Under the same reaction conditions, the diphenol selectivity over MgFe 2O 4 is higher than that over TS 1, furthermore, the reaction time is shortened greatly. The experimental phenomena can be explained by the free radical mechanism.