The metal oxides CuMnCe and CeY washcoats on cordierite were prepared using an impregnation method, and then used as support for the active Pt component to prepare the Pt/CuMnCe and Pt/CeY monolithic catalysts for the...The metal oxides CuMnCe and CeY washcoats on cordierite were prepared using an impregnation method, and then used as support for the active Pt component to prepare the Pt/CuMnCe and Pt/CeY monolithic catalysts for the deep oxidation of VOCs. In comparison with the Pt/CeY, CuMnCe, and CeY monolithic catalysts, the Pt/CuMnCe monolithic catalyst shows an excellent performance for toluene,ethyl acetate,and n-hexane oxidation and the Tis low to 216, 200 and 260 ℃,respectively. The active components Pt/PtO and CuMnCe result in a better synergetic interaction, which promote the catalyst reducibility, increase the oxygen mobility, and enhance the adsorption and activation of organic molecules.展开更多
A monolithic series of Cu-Mn-Ce oxides supported on cordierites with different Cu/Mn/Ce molar ratios were prepared by the in-situ sol-gel method without any binder. The catalysts were characterized by scanning electro...A monolithic series of Cu-Mn-Ce oxides supported on cordierites with different Cu/Mn/Ce molar ratios were prepared by the in-situ sol-gel method without any binder. The catalysts were characterized by scanning electron microscopy （SEM）, energy dispersive spectrometer （EDS）, X-ray diffraction （XRD）, and Brunauer-Emmett-Teller method （BET） and examined in the catalytic combustion of volatile organic compounds （VOCs）. The results showed that the well-dispersed nanometer particles of mixed oxides adhered firmly to the cordierite surface. Cu0.15Mn0.3Ce55/cordierite was identified as the most active catalyst. Compared with commercial Pd/Al2O3, Cu0.15Mn0.3Ce55/cordierite showed higher activities for the combustion of various types of VOCs, especially for oxy-derivative compounds which could be lighted off below 200 ℃.展开更多
The catalysts of iron-doped Mn-Ce/TiO2 （Fe-Mn-Ce/TiO2） prepared by sol-gel method were investigated for low temperature selective catalytic reduction （SCR） of NO with NH3. It was found that the NO conversion over ...The catalysts of iron-doped Mn-Ce/TiO2 （Fe-Mn-Ce/TiO2） prepared by sol-gel method were investigated for low temperature selective catalytic reduction （SCR） of NO with NH3. It was found that the NO conversion over Fe-Mn-Ce/TiO2 was obviously improved after iron doping compared with that over Mn-Ce/TiO2. Fe-Mn-Ce/TiO2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity. The results showed that 96.8% NO conversion was obtained over Fe（0.1）-Mn-Ce/TiO2 at 180~C at a space velocity of 50,000 hr-1. Fe-Mn-Ce/TiO2 exhibited much higher resistance to H2O and SO2 than that of Mn-Ce/TiO2. The properties of the catalysts were characterized using X-ray diffraction （XRD）, N2 adsorption, temperature programmed desorption （NH3-TPD and NOx-TPD）, and X- ray photoelectron spectroscopy （XPS） techniques. BET, NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping. It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe^3＋ state. The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts. The oxygen concentrations on the surface of the catalysts were found to increase after iron doping. Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H20 and SO2.展开更多
Among multitudinous metal‐oxide catalysts for the selective catalytic reduction of NOx with NH3(NH3‐SCR),Mn‐based catalysts have become very popular and developed rapidly in recent years because of its superior low...Among multitudinous metal‐oxide catalysts for the selective catalytic reduction of NOx with NH3(NH3‐SCR),Mn‐based catalysts have become very popular and developed rapidly in recent years because of its superior low‐temperature denitrification activity,mainly originating from multi‐valence of Mn.Most studies suggest that the catalytic activity of multi‐component oxides is superior to that of single‐component catalysts owing to the synergistic effect among the metallic elements in such materials,of which more attentions have been given to Ce as an additive owing to its powerful oxygen storage capacity,redox ability and its ready availability.As the core of SCR technology,the research points in catalyst development at the present stage of all researchers in countries mainly centralize on the optimization of active components,carriers,calcination temperature,calcination time and temperature‐raising procedure,giving little thought to the effects of the calcination atmosphere.In the present work,Ce‐modified Mn‐based catalysts were prepared by a simple impregnation method.The effects of the calcination atmosphere(N2,air or O2)on the performance of the resulting materials during NH3‐SCR and its causes of the differences were subsequently investigated and characterized using various analytical methods.Data obtained from X‐ray diffraction,thermogravimetry and temperature‐programmed reduction with hydrogen show that calcination under N2reduces both the degree of oxidation and crystallization of the MnOx.Scanning electron microscopy also demonstrates that the use of N2inhibits the growth of grains and increases the dispersion of the catalysts.In addition,the results of temperature‐programmed desorption with ammonia indicate that catalysts calcined under N2exhibit a greater quantity of acid sites.Finally,X‐ray photoelectron spectrometry and activity results demonstrate that MnOx in the lower valence states is more favorable for NH3‐SCR reactions.In conclusion,catalysts calcined under N2show superior performance during NH3‐SCR for NOx removal,allowing NO conversions up to94%at473K.展开更多
SO2 poisoning and regeneration of Mn-Ce/TiO2 catalyst prepared by a novel co-precipitation method for low temperature selective catalytic reduction （SCR） of NOx with ammonia were investigated in this study. When 700...SO2 poisoning and regeneration of Mn-Ce/TiO2 catalyst prepared by a novel co-precipitation method for low temperature selective catalytic reduction （SCR） of NOx with ammonia were investigated in this study. When 700 ppm SO2 was fed in, the Mn-Ce/TiO2 catalyst had good resistance to SO2, but the deactivation of Mn-Ce/TiO2 poisoned by SO2 still occurred. The NO conversion of Mn-Ce/TiO2 （the molar ra-tio of Ce to Ti is 0.075） catalyst decreased from 92.5% to 34.6% in 13 h. Characterizations of fresh and SO2-poisoned Mn-Ce/TiO2 catalysts were carried out by Brunauer-Emmett-Teller method （BET）, ion chromatography （IC）, X-ray photoelectron spectroscopy （XPS）, and X-ray diffraction （XRD）. The characterized results indicated that the deposition of sulfates and nitrates on the surface made the catalyst deactivated. Water washing, thermal regeneration and reductive regeneration were used to regenerate the deactivated Mn-Ce/TiO2. And water washing showed best performance on the regeneration of poisoned catalysts, especially with ultrasonic vibration. The Mn-Ce/TiO2 catalyst showed high stability under a series of deactivation-regeneration experiments for ten cycles.展开更多
采用高温固相法制备了SrZrSi_(2)O_(7):Ce^(3+),Mn^(2+)荧光粉。通过X射线衍射(X-ray Power Diffractometer,XRD)、激发和发射光谱及电子显微分析对材料的分子结构、显微形貌、发光特性和能量传递机理进行了研究。结果表明,荧光粉的主...采用高温固相法制备了SrZrSi_(2)O_(7):Ce^(3+),Mn^(2+)荧光粉。通过X射线衍射(X-ray Power Diffractometer,XRD)、激发和发射光谱及电子显微分析对材料的分子结构、显微形貌、发光特性和能量传递机理进行了研究。结果表明,荧光粉的主晶相是单斜晶系的SrZrSi_(2)O_(7),Ce^(3+)离子和Mn^(2+)离子占据一部分Sr^(2+)离子的晶体学格位。在296 nm激发下,可以观察到来自Ce^(3+)离子的蓝光发射峰,归属于Ce^(3+)离子的5d→4f能级跃迁。在544 nm处,有来自Mn^(2+)离子的绿光发射峰,归因于Mn^(2+)离子的^(4)T_(1)(4G)-^(6)A_(1)(6S)自旋禁止跃迁,表明发生了从Ce^(3+)离子到Mn^(2+)离子的能量传递过程,为设计蓝光到绿光之间可控制备的新型荧光粉提供了理论和实验的信息。展开更多
A series of Ce-doped MnOx/TiO2 catalysts were prepared by impregnation method and used for catalytic oxidation of NO in the presence of excess O2. The sample with the Ce doping concentration of Ce/Mn=l/3 and calcined ...A series of Ce-doped MnOx/TiO2 catalysts were prepared by impregnation method and used for catalytic oxidation of NO in the presence of excess O2. The sample with the Ce doping concentration of Ce/Mn=l/3 and calcined at 300 ℃ shows a superior activity for NO oxidation to NO2. On Ce（1）Mn（3）Ti catalyst, 58% NO conversion was obtained at 200 ℃ and 85% NO conversion at 250 ℃ with a GHSV of 41000 h-1, which was much higher than that over MnOx/TiO2 catalyst （48% at 250 ℃）. Characterization results implied that the higher activity of Ce（1）Mn（3）Ti could be attributed to the enrichment of well-dispersed MnO2 on the surface and the abundance of Mn3＋ and Zi3＋ species. The addition of Ce into MnO2/TiO2 could improve oxygen storage capacity and facilitate oxygen mobility of the catalyst as shown by PL and ESR, so that its activity for NO oxidation could be enhanced. The effect of H2O and SO2 on the catalyst activity was also investigated.展开更多
A series of Mn-Cu mixed oxide catalysts were prepared by precipitation method. The catalysts were characterized by N2 adsorp- tion-desorption, H2-TPR and XPS. When the loading ratio of manganese oxides to copper oxide...A series of Mn-Cu mixed oxide catalysts were prepared by precipitation method. The catalysts were characterized by N2 adsorp- tion-desorption, H2-TPR and XPS. When the loading ratio of manganese oxides to copper oxides was 8：2 or 7：3, the catalysts possessed better catalytic activity, and benzene was converted completely at 558 K. Results of H2-TPR showed that the loading of a small amount of copper oxides decreased the reduction temperature of catalysts. Results of XPS showed that the loading of a small amount of copper oxides increased the proportion of manganese and defective oxygen on the surface of catalysts, and stabilized manganese at higher oxidation state. And the catalyst with the loading ratio 7：3 was a little worse than 8：2, since the interaction between manganese oxides and copper oxides is too strong, copper oxides migrate to the surface of catalysts and manganese oxides in excess are immerged.展开更多
Ce-modified Mn-Fe mixed-oxide catalysts were prepared by a citric acid sol-gel method and characterized by X-ray diffraction,Raman,N2 adsorption-desorption,infrared spectra H2 temperature-programmed reduction and ther...Ce-modified Mn-Fe mixed-oxide catalysts were prepared by a citric acid sol-gel method and characterized by X-ray diffraction,Raman,N2 adsorption-desorption,infrared spectra H2 temperature-programmed reduction and thermogravimetric analyses.Their catalytic properties were investigated in ozone(O3)decomposition reaction.Results show that the small amount of rare earth metal Ce added during Mn-Fe(FM) mixed-oxide synthesis greatly improves the catalytic performance in O3 decomposition.Among the prepared catalysts.the C0.04(FM)0.96 mixed-oxide catalyst exhibits the highest catalytic activity and stability.The O3 conversion over C0.04(FM)0.96 is 98% after 24 h reaction at 25℃ under dry condition,and that over FM decreases to 90% after 16 h reaction.At 0℃,the O3 conversion over C0.04(FM)0.96 is 95% after 7 h reaction under dry condition.and that over FM slows down to 70%.Under humid condition(RH 65%),the O3 conversion over C0.04(FM)0.96 is 63% after 6.5 h reaction at 25℃.while that over FM decreases to 55%.When Ce is doped into Mn-Fe mixed oxides,the small amount of Ce enters the crystal lattice of MnO2.and partial Fe is separated to form Fe2O3.This changes cause lattice distortion and increase defects and enable the as-synthesized Ce-Fe-Mn ternary mixed-oxide catalysts to acquire additional oxygen vacancies and increase their specific surface area,thereby increasing the number of reaction sites and enhancing the catalytic performance of the catalysts for O3 decomposition.展开更多
Cu-Mn, Cu-Mn-Ce, and Cu-Ce mixed-oxide catalysts were prepared by a citric acid sol-gel method and then characterized by XRD, BET, H_2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene ...Cu-Mn, Cu-Mn-Ce, and Cu-Ce mixed-oxide catalysts were prepared by a citric acid sol-gel method and then characterized by XRD, BET, H_2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu-Mn-Ce ternary mixed-oxide catalyst with 1：2：4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu-Mn-Ce catalyst, a portion of Cu and Mn species entered into the Ce O2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu-Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu-Mn and Cu-Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.展开更多
The catalytic diesel particulate filter(CDPF)is the most widely used after-treatment device for controlling diesel engine soot emissions.The development of cost-effective catalysts is crucial for diesel engines to com...The catalytic diesel particulate filter(CDPF)is the most widely used after-treatment device for controlling diesel engine soot emissions.The development of cost-effective catalysts is crucial for diesel engines to comply with future ultra-low emission regulations.This paper studies a new type of Ce/La modified Cs-V non-noble metal CDPF catalyst.Three test catalysts(Cs-V,Cs-V-5%Ce,and Cs-V-5%La)were formulated to explore the physical properties,activity,and sulfur resistance through XRD,SEM,XPS,and TPO tests.And TGA tests with different catalyst-to-soot mass ratios were designed to analyze the reaction kinetics.The results show that the soot oxidation process is divided into three stages:slow oxidation,rapid oxidation,and soot burnout.SEM and XRD results show that,compared with Ce doping,La-doped catalysts have less damage to the microstructure of the first active component,Cs_(2)V_(4)O_(11).XPS results show that the introduction of Ce and La is beneficial to the formation of oxygen vacancies and lattice distortion,increasing the proportion of active oxygen species,thereby improving the soot oxidation activity,among which La-doped active oxygen species have the highest proportion(94%).And the Cs-V-5%La catalyst has the best effect on improving the soot conversion of the three stages.The fresh state has the best low-temperature activity index,the lowest characteristic temperature(T_(50) of 374℃)and activation energy(115.01 kJ/mol),and excellent sulfur resistance.The soot conversion and oxidation speed of the three stages decreases,duration lengthens,and activation energy increases by more than 100 kJ/mol as catalyst-to-soot mass ratios decrease.展开更多
The effect of Au on the reducibility of La Ce Mn catalyst was studied in the synthetic exhaust gas mixture containing 10% oxygen. The characteristics of samples were analyzed by BET, SEM, XRD and activity evaluation...The effect of Au on the reducibility of La Ce Mn catalyst was studied in the synthetic exhaust gas mixture containing 10% oxygen. The characteristics of samples were analyzed by BET, SEM, XRD and activity evaluation. The results show that, in lean combustion, the performance of perovskite type catalysts is evidently enhanced through adding Au, and specially a satisfying reducibility for NO x is demonstrated between 300～500 ℃. The catalytic activity of samples increases with the loading amount of Au, and the maximum conversion rate for NO x decomposition reaches up to 47% in 360～400 ℃. Moreover, the dispersivity and uniformity of the surface distribution of perovskite with Au have an important influence on the catalytic activity.展开更多
Transition metals doped Mn-based catalysts were prepared via ultrasonic immersing method for the selective catalytic reduction (SCR) of NOx from fuel gas. The Catalysts’ DeNOx efficiency and tolerance to sulfur were ...Transition metals doped Mn-based catalysts were prepared via ultrasonic immersing method for the selective catalytic reduction (SCR) of NOx from fuel gas. The Catalysts’ DeNOx efficiency and tolerance to sulfur were investigated in the paper. XRD results demonstrate high dispersion of Mn, Ce and M (Pr, Y, Zr, W) elements on TiO2 carrier, which is favor for reduction of active materials content. Mn-Ce-W catalyst presents uniform particle size about 500 nm to 800 nm from SEM pictures and shows the best NOx conversion of 93.2% at 200°C and 98.4% at 250°C, respectively. Sulfur tolerance analysis indicated that transition metals M can improve the catalysts’ performance when 0.01% SO2 exists in the fuel gas, because metal doping into the Mn-Ce catalyst can inhibit the sulfate deposition, especially metal sulfate, on the catalyst, which can be seen from the Fourier infrared spectrum.展开更多
A series of Mn-doped K-Co-Mo catalysts were prepared by a sol-gel method. The catalyst structure was well characterized by X-ray diffraction, N2 physisorption, NH3 temperature- programmed adsorption, in situ diffuse r...A series of Mn-doped K-Co-Mo catalysts were prepared by a sol-gel method. The catalyst structure was well characterized by X-ray diffraction, N2 physisorption, NH3 temperature- programmed adsorption, in situ diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption fine structure spectroscopy. The catalytic performance for higher alcohol synthesis from syngas was measured. It was found that the Mn-doped catalysts ex- hibited a much higher activity as compared to the unpromoted catalyst, and in particular the C2＋ alcohol selectivity increased significantly. The distribution of alcohol products de- viated from the Anderson-Schulz-Flory law. The portion of methanol in total alcohol was suppressed remarkably and the ethanol became the predominant product. Characterization results indicated that the incorporation of Mn enhanced the interaction of Co and Mo and thus led to the formation of Co-Mo-O species, which was regarded as the active site for the alcohol synthesis. Secondly, the presence of Mn reduced the amount of strong acid sites significantly and meanwhile promoted the formation of weak acid sites, which had a positive effect on the synthesis of alcohol. Furthermore, it was found that the incorporation of Mn can enhance the adsorption of linear- and bridge-type CO significantly, which contributed to the formation of alcohol and growth of carbon chain and thus increased the selectivity to C2＋OH.展开更多
基金Project supported by the National Natural Science Foundation of China(21506194,21676255)the Natural Science Foundation of Zhejiang Province(Y16B070011)the Commission of Science and Technology of Zhejiang Province(2017C03007,2017C33106)
文摘The metal oxides CuMnCe and CeY washcoats on cordierite were prepared using an impregnation method, and then used as support for the active Pt component to prepare the Pt/CuMnCe and Pt/CeY monolithic catalysts for the deep oxidation of VOCs. In comparison with the Pt/CeY, CuMnCe, and CeY monolithic catalysts, the Pt/CuMnCe monolithic catalyst shows an excellent performance for toluene,ethyl acetate,and n-hexane oxidation and the Tis low to 216, 200 and 260 ℃,respectively. The active components Pt/PtO and CuMnCe result in a better synergetic interaction, which promote the catalyst reducibility, increase the oxygen mobility, and enhance the adsorption and activation of organic molecules.
基金Project supported by National Natural Science Foundation of China (21107096)Zhejiang Provincial Natural Science Foundation (Y5090202)
文摘A monolithic series of Cu-Mn-Ce oxides supported on cordierites with different Cu/Mn/Ce molar ratios were prepared by the in-situ sol-gel method without any binder. The catalysts were characterized by scanning electron microscopy （SEM）, energy dispersive spectrometer （EDS）, X-ray diffraction （XRD）, and Brunauer-Emmett-Teller method （BET） and examined in the catalytic combustion of volatile organic compounds （VOCs）. The results showed that the well-dispersed nanometer particles of mixed oxides adhered firmly to the cordierite surface. Cu0.15Mn0.3Ce55/cordierite was identified as the most active catalyst. Compared with commercial Pd/Al2O3, Cu0.15Mn0.3Ce55/cordierite showed higher activities for the combustion of various types of VOCs, especially for oxy-derivative compounds which could be lighted off below 200 ℃.
基金supported by the National Natural Science Foundation of China (No. 90610018,50976050)the New Century Excellent Talents in University (No. NCET-07-0457)the National Key Technologies R&D Program of Tianjin (No. 09ZCKFSH01900)
文摘The catalysts of iron-doped Mn-Ce/TiO2 （Fe-Mn-Ce/TiO2） prepared by sol-gel method were investigated for low temperature selective catalytic reduction （SCR） of NO with NH3. It was found that the NO conversion over Fe-Mn-Ce/TiO2 was obviously improved after iron doping compared with that over Mn-Ce/TiO2. Fe-Mn-Ce/TiO2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity. The results showed that 96.8% NO conversion was obtained over Fe（0.1）-Mn-Ce/TiO2 at 180~C at a space velocity of 50,000 hr-1. Fe-Mn-Ce/TiO2 exhibited much higher resistance to H2O and SO2 than that of Mn-Ce/TiO2. The properties of the catalysts were characterized using X-ray diffraction （XRD）, N2 adsorption, temperature programmed desorption （NH3-TPD and NOx-TPD）, and X- ray photoelectron spectroscopy （XPS） techniques. BET, NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping. It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe^3＋ state. The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts. The oxygen concentrations on the surface of the catalysts were found to increase after iron doping. Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H20 and SO2.
文摘Among multitudinous metal‐oxide catalysts for the selective catalytic reduction of NOx with NH3(NH3‐SCR),Mn‐based catalysts have become very popular and developed rapidly in recent years because of its superior low‐temperature denitrification activity,mainly originating from multi‐valence of Mn.Most studies suggest that the catalytic activity of multi‐component oxides is superior to that of single‐component catalysts owing to the synergistic effect among the metallic elements in such materials,of which more attentions have been given to Ce as an additive owing to its powerful oxygen storage capacity,redox ability and its ready availability.As the core of SCR technology,the research points in catalyst development at the present stage of all researchers in countries mainly centralize on the optimization of active components,carriers,calcination temperature,calcination time and temperature‐raising procedure,giving little thought to the effects of the calcination atmosphere.In the present work,Ce‐modified Mn‐based catalysts were prepared by a simple impregnation method.The effects of the calcination atmosphere(N2,air or O2)on the performance of the resulting materials during NH3‐SCR and its causes of the differences were subsequently investigated and characterized using various analytical methods.Data obtained from X‐ray diffraction,thermogravimetry and temperature‐programmed reduction with hydrogen show that calcination under N2reduces both the degree of oxidation and crystallization of the MnOx.Scanning electron microscopy also demonstrates that the use of N2inhibits the growth of grains and increases the dispersion of the catalysts.In addition,the results of temperature‐programmed desorption with ammonia indicate that catalysts calcined under N2exhibit a greater quantity of acid sites.Finally,X‐ray photoelectron spectrometry and activity results demonstrate that MnOx in the lower valence states is more favorable for NH3‐SCR reactions.In conclusion,catalysts calcined under N2show superior performance during NH3‐SCR for NOx removal,allowing NO conversions up to94%at473K.
基金financially supported by the Research Project of China Guodian Corporation (No.D11T22)
文摘SO2 poisoning and regeneration of Mn-Ce/TiO2 catalyst prepared by a novel co-precipitation method for low temperature selective catalytic reduction （SCR） of NOx with ammonia were investigated in this study. When 700 ppm SO2 was fed in, the Mn-Ce/TiO2 catalyst had good resistance to SO2, but the deactivation of Mn-Ce/TiO2 poisoned by SO2 still occurred. The NO conversion of Mn-Ce/TiO2 （the molar ra-tio of Ce to Ti is 0.075） catalyst decreased from 92.5% to 34.6% in 13 h. Characterizations of fresh and SO2-poisoned Mn-Ce/TiO2 catalysts were carried out by Brunauer-Emmett-Teller method （BET）, ion chromatography （IC）, X-ray photoelectron spectroscopy （XPS）, and X-ray diffraction （XRD）. The characterized results indicated that the deposition of sulfates and nitrates on the surface made the catalyst deactivated. Water washing, thermal regeneration and reductive regeneration were used to regenerate the deactivated Mn-Ce/TiO2. And water washing showed best performance on the regeneration of poisoned catalysts, especially with ultrasonic vibration. The Mn-Ce/TiO2 catalyst showed high stability under a series of deactivation-regeneration experiments for ten cycles.
文摘采用高温固相法制备了SrZrSi_(2)O_(7):Ce^(3+),Mn^(2+)荧光粉。通过X射线衍射(X-ray Power Diffractometer,XRD)、激发和发射光谱及电子显微分析对材料的分子结构、显微形貌、发光特性和能量传递机理进行了研究。结果表明,荧光粉的主晶相是单斜晶系的SrZrSi_(2)O_(7),Ce^(3+)离子和Mn^(2+)离子占据一部分Sr^(2+)离子的晶体学格位。在296 nm激发下,可以观察到来自Ce^(3+)离子的蓝光发射峰,归属于Ce^(3+)离子的5d→4f能级跃迁。在544 nm处,有来自Mn^(2+)离子的绿光发射峰,归因于Mn^(2+)离子的^(4)T_(1)(4G)-^(6)A_(1)(6S)自旋禁止跃迁,表明发生了从Ce^(3+)离子到Mn^(2+)离子的能量传递过程,为设计蓝光到绿光之间可控制备的新型荧光粉提供了理论和实验的信息。
基金supported by the National Natural Science Foundation of China (Grant No. 51078185)
文摘A series of Ce-doped MnOx/TiO2 catalysts were prepared by impregnation method and used for catalytic oxidation of NO in the presence of excess O2. The sample with the Ce doping concentration of Ce/Mn=l/3 and calcined at 300 ℃ shows a superior activity for NO oxidation to NO2. On Ce（1）Mn（3）Ti catalyst, 58% NO conversion was obtained at 200 ℃ and 85% NO conversion at 250 ℃ with a GHSV of 41000 h-1, which was much higher than that over MnOx/TiO2 catalyst （48% at 250 ℃）. Characterization results implied that the higher activity of Ce（1）Mn（3）Ti could be attributed to the enrichment of well-dispersed MnO2 on the surface and the abundance of Mn3＋ and Zi3＋ species. The addition of Ce into MnO2/TiO2 could improve oxygen storage capacity and facilitate oxygen mobility of the catalyst as shown by PL and ESR, so that its activity for NO oxidation could be enhanced. The effect of H2O and SO2 on the catalyst activity was also investigated.
基金Project supported by National Natural Science Foundation of China (20773090)the National High Technology Research and Development Program of China (863 Program, 2006AA06Z347)the Youth Fund of Sichuan University (2008119)
文摘A series of Mn-Cu mixed oxide catalysts were prepared by precipitation method. The catalysts were characterized by N2 adsorp- tion-desorption, H2-TPR and XPS. When the loading ratio of manganese oxides to copper oxides was 8：2 or 7：3, the catalysts possessed better catalytic activity, and benzene was converted completely at 558 K. Results of H2-TPR showed that the loading of a small amount of copper oxides decreased the reduction temperature of catalysts. Results of XPS showed that the loading of a small amount of copper oxides increased the proportion of manganese and defective oxygen on the surface of catalysts, and stabilized manganese at higher oxidation state. And the catalyst with the loading ratio 7：3 was a little worse than 8：2, since the interaction between manganese oxides and copper oxides is too strong, copper oxides migrate to the surface of catalysts and manganese oxides in excess are immerged.
基金supported by the National Natural Science Foundation of China(21506194,21676255)the Natural Science Foundation of Zhejiang Province(Y16B070011)the Commission of Science and Technology of Zhejiang province(2017C03007,2017C33106).
文摘Ce-modified Mn-Fe mixed-oxide catalysts were prepared by a citric acid sol-gel method and characterized by X-ray diffraction,Raman,N2 adsorption-desorption,infrared spectra H2 temperature-programmed reduction and thermogravimetric analyses.Their catalytic properties were investigated in ozone(O3)decomposition reaction.Results show that the small amount of rare earth metal Ce added during Mn-Fe(FM) mixed-oxide synthesis greatly improves the catalytic performance in O3 decomposition.Among the prepared catalysts.the C0.04(FM)0.96 mixed-oxide catalyst exhibits the highest catalytic activity and stability.The O3 conversion over C0.04(FM)0.96 is 98% after 24 h reaction at 25℃ under dry condition,and that over FM decreases to 90% after 16 h reaction.At 0℃,the O3 conversion over C0.04(FM)0.96 is 95% after 7 h reaction under dry condition.and that over FM slows down to 70%.Under humid condition(RH 65%),the O3 conversion over C0.04(FM)0.96 is 63% after 6.5 h reaction at 25℃.while that over FM decreases to 55%.When Ce is doped into Mn-Fe mixed oxides,the small amount of Ce enters the crystal lattice of MnO2.and partial Fe is separated to form Fe2O3.This changes cause lattice distortion and increase defects and enable the as-synthesized Ce-Fe-Mn ternary mixed-oxide catalysts to acquire additional oxygen vacancies and increase their specific surface area,thereby increasing the number of reaction sites and enhancing the catalytic performance of the catalysts for O3 decomposition.
基金the financial support from the Natural Science Foundation of China (No. 21107096)Zhejiang Provincial Natural Science Foundation of China (No. Y14E080008)+1 种基金the Commission of Science and Technology of Zhejiang province (No. 2013C03021)the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20133317110004)
文摘Cu-Mn, Cu-Mn-Ce, and Cu-Ce mixed-oxide catalysts were prepared by a citric acid sol-gel method and then characterized by XRD, BET, H_2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu-Mn-Ce ternary mixed-oxide catalyst with 1：2：4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu-Mn-Ce catalyst, a portion of Cu and Mn species entered into the Ce O2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu-Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu-Mn and Cu-Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.
基金supported by the National Natural Science Foundation of China(No.52206167)the Science and Technology Talents and Platform Program(Academician ExpertWorkstation)(No.202305AF150109)+1 种基金Shanghai Sailing Program(No.21YF1448900)the Introduced and co-builded high-level research and development institutions of Jiangxi Province(No.20212CCH45004).
文摘The catalytic diesel particulate filter(CDPF)is the most widely used after-treatment device for controlling diesel engine soot emissions.The development of cost-effective catalysts is crucial for diesel engines to comply with future ultra-low emission regulations.This paper studies a new type of Ce/La modified Cs-V non-noble metal CDPF catalyst.Three test catalysts(Cs-V,Cs-V-5%Ce,and Cs-V-5%La)were formulated to explore the physical properties,activity,and sulfur resistance through XRD,SEM,XPS,and TPO tests.And TGA tests with different catalyst-to-soot mass ratios were designed to analyze the reaction kinetics.The results show that the soot oxidation process is divided into three stages:slow oxidation,rapid oxidation,and soot burnout.SEM and XRD results show that,compared with Ce doping,La-doped catalysts have less damage to the microstructure of the first active component,Cs_(2)V_(4)O_(11).XPS results show that the introduction of Ce and La is beneficial to the formation of oxygen vacancies and lattice distortion,increasing the proportion of active oxygen species,thereby improving the soot oxidation activity,among which La-doped active oxygen species have the highest proportion(94%).And the Cs-V-5%La catalyst has the best effect on improving the soot conversion of the three stages.The fresh state has the best low-temperature activity index,the lowest characteristic temperature(T_(50) of 374℃)and activation energy(115.01 kJ/mol),and excellent sulfur resistance.The soot conversion and oxidation speed of the three stages decreases,duration lengthens,and activation energy increases by more than 100 kJ/mol as catalyst-to-soot mass ratios decrease.
文摘The effect of Au on the reducibility of La Ce Mn catalyst was studied in the synthetic exhaust gas mixture containing 10% oxygen. The characteristics of samples were analyzed by BET, SEM, XRD and activity evaluation. The results show that, in lean combustion, the performance of perovskite type catalysts is evidently enhanced through adding Au, and specially a satisfying reducibility for NO x is demonstrated between 300～500 ℃. The catalytic activity of samples increases with the loading amount of Au, and the maximum conversion rate for NO x decomposition reaches up to 47% in 360～400 ℃. Moreover, the dispersivity and uniformity of the surface distribution of perovskite with Au have an important influence on the catalytic activity.
文摘Transition metals doped Mn-based catalysts were prepared via ultrasonic immersing method for the selective catalytic reduction (SCR) of NOx from fuel gas. The Catalysts’ DeNOx efficiency and tolerance to sulfur were investigated in the paper. XRD results demonstrate high dispersion of Mn, Ce and M (Pr, Y, Zr, W) elements on TiO2 carrier, which is favor for reduction of active materials content. Mn-Ce-W catalyst presents uniform particle size about 500 nm to 800 nm from SEM pictures and shows the best NOx conversion of 93.2% at 200°C and 98.4% at 250°C, respectively. Sulfur tolerance analysis indicated that transition metals M can improve the catalysts’ performance when 0.01% SO2 exists in the fuel gas, because metal doping into the Mn-Ce catalyst can inhibit the sulfate deposition, especially metal sulfate, on the catalyst, which can be seen from the Fourier infrared spectrum.
文摘A series of Mn-doped K-Co-Mo catalysts were prepared by a sol-gel method. The catalyst structure was well characterized by X-ray diffraction, N2 physisorption, NH3 temperature- programmed adsorption, in situ diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption fine structure spectroscopy. The catalytic performance for higher alcohol synthesis from syngas was measured. It was found that the Mn-doped catalysts ex- hibited a much higher activity as compared to the unpromoted catalyst, and in particular the C2＋ alcohol selectivity increased significantly. The distribution of alcohol products de- viated from the Anderson-Schulz-Flory law. The portion of methanol in total alcohol was suppressed remarkably and the ethanol became the predominant product. Characterization results indicated that the incorporation of Mn enhanced the interaction of Co and Mo and thus led to the formation of Co-Mo-O species, which was regarded as the active site for the alcohol synthesis. Secondly, the presence of Mn reduced the amount of strong acid sites significantly and meanwhile promoted the formation of weak acid sites, which had a positive effect on the synthesis of alcohol. Furthermore, it was found that the incorporation of Mn can enhance the adsorption of linear- and bridge-type CO significantly, which contributed to the formation of alcohol and growth of carbon chain and thus increased the selectivity to C2＋OH.
