CN102728388B - Single crystal Ag nanoplate/Co3O4/Eu0.6Sr0.4FeO3 composite catalyst, preparation thereof and application thereof - Google Patents

Single crystal Ag nanoplate/Co3O4/Eu0.6Sr0.4FeO3 composite catalyst, preparation thereof and application thereof Download PDF

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CN102728388B
CN102728388B CN201210212461.6A CN201210212461A CN102728388B CN 102728388 B CN102728388 B CN 102728388B CN 201210212461 A CN201210212461 A CN 201210212461A CN 102728388 B CN102728388 B CN 102728388B
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monocrystalline
feo
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nanometer sheet
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CN102728388A (en
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戴洪兴
吉科猛
邓积光
王媛
谢少华
李欣尉
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Beijing University of Technology
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Beijing University of Technology
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Abstract

The invention relates to a single crystal Ag nanoplate/Co3O4/Eu0.6Sr0.4FeO3 composite catalyst, a preparation thereof and an application thereof, which belongs to the composite catalyst technical field. The single crystal Ag nanoplate/Co3O4/Eu0.6Sr0.4FeO3 composite catalyst is loaded on the pore channel and the surface of Co3O4/Eu0.6Sr0.4FeO3; 4mmol/L of AgNO3 solution and 6.0mmol/L NaBH4 solution are prepared according to the mol ratio of 1: 15: 0.7 of AgNO3, citric acid to PVP; 3DOM Co3O4/Eu0.6S r0.4FeO3 is dipped in the AgNO3 solution, a NaBH4 solution is added according the mol ratio of 1: 6 of AgNO3 to NaBH4, and then the mixture is rapidly transferred to a rotary evaporation instrument when the concussion is carried out, and rotated and stirred at the room temperature for 60 minutes, filtered, washed, and dried at the room temperature to obtain the catalyst. The loaded sample presents more excellent catalytic performance on a toluene oxidation reaction at a low conversion rate phase.

Description

Monocrystalline Ag nanometer sheet/Co 3o 4/ Eu 0.6sr 0.4feO 3composite catalyst, preparation and application
Technical field
The present invention relates to a kind of support type composite catalyst monocrystalline Ag nanometer sheet/Co of three-dimensional ordered macroporous structure 3o 4/ Eu 0.6sr 0.4feO 3, the silver sol original position load preparation method of this catalyst, and application aspect catalytic combustion elimination effumability organic pollution (VOCs), belong to composite catalyst technical field.
Background technology
Three-dimensional ordered macroporous structure (3DOM) perofskite type oxide material (ABO 3) because it has larger specific area, flourishing pore structure, higher stability, the designability of chemical component and good magnetic electricity performance, all there is in a lot of fields larger application potential, especially being widely studied at heterogeneous catalysis field its preparation method and catalytic performance, is mainly that the glue crystal template of the ordered 3 D structure that is piled into polyethylene microballoon or poly (methyl methacrylate) micro-sphere is standby by nano-copy legal system.At present, the perofskite type oxide of multiple 3DOM structure is synthesized out, as LaFeO 3(M.Sadakane et al., CHEMISTRYOF MATERIALS, 2005,17:3546-3551), LaCoO 3(J.F.Xu et al., JOURNAL OFCATALYSIS, 2011,282:1-12), LaMnO 3(Y.X.Liu et al., JOURNAL OF CATALYSIS, 2012,287:149-160), SrFeO 3(K.M.Ji et al., APPLIED CATALYSIS A-GENERAL, 2012,425:153-160), EuFeO 3(Chinese invention patent, application number: 201110275386.3) and the Ca-Ti ore type material that obtains of corresponding A position or B position cation doping as La 1-xk xfeO 3and LaCo xfe 1-x0 3(J.F.Xu et al., JOURNAL OF CATALYSIS, 2011,282:1-12, CATALYSIS TODAY, 2010,153:136-142), also has the ABO about support type 3DOM in addition 3report, as utilize ultrasonic barrier diffusion method (UAMR method) to prepare the Au/LaFeO of nanogold particle load 3the CoO that prepare with equi-volume impregnating (Y.C.Wei et al., ANGEWANDTECHEMIE INTERNATIONAL EDITION, 2011,50:2326 – 2329) and this research department x/ Eu 0.6sr 0.4feO 3(Chinese invention patent, application number: 201110275386.3), and the catalytic activity of catalyst after load had more all obtained good improvement.But there is no up to now, the pertinent literature report of load monocrystal material on perovskite material both at home and abroad.In addition, not a kind of more common and more cheap noble metal still of Ag, have more as many unusual performances such as catalysis, antibacterial, conduction, heat conduction, surface enhanced Raman scattering effects, there is good application prospect at aspects such as biomaterial for medical purpose, catalysis, microelectronic circuits and photoelectric devices, particularly at catalytic field, Ag not only has good catalytic oxidation activity (but it is active in Pt and Pd), also because its good optical property is showing excellent performance equally aspect photocatalysis.Therefore the material that, has perovskite character and the special catalytic property of silver nano material concurrently if can prepare is by the meaning having very.At present; the method of preparing nano silver particles has a lot; as adopt microwave method to prepare grain Nano Silver crystalline substance (Li Mei etc.; laboratory research and exploration; 2006; 25:24-25); utilize hydrazine hydrate reduction silver nitrate to prepare nano silver particles (Zhang Yun bamboo etc., New Chemical Materials, 2006; 34:31-32); prepare nano silver particles (Wang Zhenyang etc., SCI, 2007 by ultrasonic wave auxiliary film reducing process (UAMR method); 28:1756-1758), village etc. utilizes hydrogen peroxide to pass through at normal temperatures NaBH 4reducing process is prepared triangular silver nanosheet (Chinese invention patent, grant number: CN 101947655A), Yin Yadong seminar more systematic research this kind of preparation method (Q.Zhang et al., JOURNAL OF THE AMERICANCHEMICAL SOCIETY 2011,133:18931 – 18939); Etc..In addition, account for etc. and once to utilize the displacement reaction between elemental copper and silver particles to prepare silver-colored single crystal nanoplate (Chinese invention patent, grant number: CN 101781759B) on copper product surface.
And the method for preparing catalyst that the present invention describes is: first utilize this laboratory issued patents (Chinese invention patent, application number: the support type composite catalyst CoO of the 3DOM structure 201110275386.3) x/ Eu 0.6sr 0.4feO 3preparation method prepare this kind of catalyst carrier, then use for reference the room temperature method of reducing of preparing Nano silver piece and prepare corresponding silver sol and it carried out to original position load simultaneously, prepare the 3DOM Co of monocrystalline Ag nanometer sheet load with this 3o 4/ Eu 0.6sr 0.4feO 3catalyst.In the method, adopting silver nitrate is that raw material, PVP are that surfactant and stabilizing agent, sodium borohydride are reducing agent, and the whole loading process time is shorter, the preparation of silver sol and the filtration of final products, dry all at room temperature.Representative using the toluene of more difficult catalytic oxidation as VOCs, by the active testing of prepared catalyst catalytic oxidation toluene burning is shown, the low-temperature catalytic activity of raw catalyst obtains and significantly improves after the load of monocrystal silver material.Although the at present report of the existing multiple three-dimensional ordered macroporous method for preparing catalyst for the preparation of heterogeneous catalytic oxidation of document, up to now, there is no document and patent report both at home and abroad and crosses the monocrystalline Ag nanometer sheet/Co of three-dimensional ordered macroporous structure 3o 4/ Eu 0.6sr 0.4feO 3catalyst, its preparation method and the application aspect oxidation elimination VOCs thereof.
Summary of the invention
The object of the present invention is to provide a kind of support type composite catalyst monocrystalline Ag nanometer sheet/Co that eliminates the three-dimensional ordered macroporous structure of effumability organic pollution for heterogeneous catalytic oxidation 3o 4/ Eu 0.6sr 0.4feO 3, and prepare the method for this catalyst by silver sol original position load under room temperature.The catalyst carrier CoO of the 3DOM structure adopting in the present invention x/ Eu 0.6sr 0.4feO 3according to this research department issued patents (Chinese invention patent, application number: 201110275386.3) described method preparation.
The monocrystalline Ag nanometer sheet/Co of three-dimensional ordered macroporous structure 3o 4/ Eu 0.6sr 0.4feO 3composite catalyst, is characterized in that, the Ag nanometer sheet of load is monocrystalline, at Co 3o 4/ Eu 0.6sr 0.4feO 3in surface and duct, all load has monocrystalline Ag nanometer sheet, Co 3o 4/ Eu 0.6sr 0.4feO 3monocrystalline Ag nanometer sheet in duct is less than Co 3o 4/ Eu 0.6sr 0.4feO 3the monocrystalline Ag nanometer sheet on surface.The load capacity of monocrystalline Ag nanometer sheet is controlled, preferably 1wt%-5wt%.
Monocrystalline Ag nanometer sheet/Co provided by the invention 3o 4/ Eu 0.6sr 0.4feO 3the normal temperature preparation method of composite catalyst, key step comprises: 1. by AgNO 3, citric acid, PVP(molecular weight preferably calculate by 29000) mol ratio is that 1:15:0.7 compound concentration is the AgNO of 0.4mmol/L 3solution, and the compound concentration NaBH that is 6.0mmol/L 4solution; 2. according to the demand of the percentage composition of loaded Ag on carrier, take the 3DOMCo of certain mass 3o 4/ Eu 0.6sr 0.4feO 3be immersed in the above-mentioned AgNO of certain volume 3in weak solution, after carrying complete wetting, by AgNO 3with NaBH 4mol ratio is the above-mentioned NaBH that 1:6 gets certain volume 4solution joins this AgNO 3in solution, shake while be transferred to rapidly on Rotary Evaporators, 60min is stirred in room temperature rotation; 3. reacted rear slow filtration, and the material obtaining has been washed by deionized water, drying at room temperature, obtains the monocrystalline Ag nanometer sheet/Co of three-dimensional ordered macroporous structure 3o 4/ Eu 0.6sr 0.4feO 3composite catalyst.
In order to obtain more large single crystal Ag nanometer sheet, wherein the 2. step add a certain amount of 30wt.% hydrogen peroxide, can be by 1ml AgNO 3solution adds 0.01mL30wt.% hydrogen peroxide, and this reaction time is 30min, and other step is identical.
The monocrystalline Ag nanometer sheet preferred thickness of above-mentioned preparation is 3 ~ 5 nanometers, out-of-shape, and big or small heterogeneity, the silver strip (being about 50nm) that diameter is less is attached on carrier hole wall, and the silver strip that diameter is larger is distributed in carrier surface; Add hydrogen peroxide in step (1) after, silver strip becomes large, and the silver strip that is distributed in carrier surface increases increase, and the silver strip being distributed on hole wall reduces.Toluene concentration be 1000ppm, toluene/oxygen mol ratio be 1/400 and air speed be that (g is h) under condition, and when toluene conversion is lower than 30% time, the catalyst that the method is prepared makes toluene conversion improve about 6-12% than raw catalyst for 20000mL/.
Utilize crystal structure, particle morphology and the catalytic activity to toluene of the Instrument measuring gained target products such as D8ADVANCE type X-ray diffractometer (XRD), ZEISS SUPRA 55 type SEM (SEM), JEOL-2010 type transmission electron microscope (TEM), gas-chromatography GC-2010.Result shows, adopts method described in the present invention to make the Co into the three-dimensional ordered macroporous structure of monocrystalline Ag nanometer sheet load 3o 4/ Eu 0.6sr 0.4feO 3, after load, to toluene oxidation, reaction demonstrates better catalytic performance in the low-conversion stage to sample.
Accompanying drawing explanation
For further explanation the present invention, elaborate with embodiment below, and provide accompanying drawing and describe the 3DOM Co of the monocrystalline Ag nanometer sheet load that the present invention obtains 3o 4/ Eu 0.6sr 0.4feO 3.Wherein:
Fig. 1 is the XRD spectra of prepared sample, and wherein figure (a), (b), (c) are respectively gained sample and raw catalyst carrier 3DOM Co in embodiment 1, embodiment 2 3o 4/ Eu 0.6sr 0.4feO 3corresponding XRD spectra.
Fig. 2 is SEM (a, the d, g) and TEM (b, c, e, f, h) electromicroscopic photograph of obtained sample, wherein figure (a-c) is the corresponding electromicroscopic photograph of sample in embodiment 1, figure (d-f) is the corresponding electromicroscopic photograph of sample in embodiment 2, (g-h) is 3DOM Co 3o 4/ Eu 0.6sr 0.4feO 3corresponding electromicroscopic photograph.
Fig. 3 is the catalytic activity curve of obtained sample to the toluene oxidation low-conversion stage, and wherein curve (a), (b), (c) are respectively embodiment 1, embodiment 2 and 3DOM Co 3o 4/ Eu 0.6sr 0.4feO 3the catalytic activity curve of gained sample.
The specific embodiment
Embodiment 1: 1. by 0.0068g silver nitrate (AgNO 3), 0.1261g citric acid and 0.8120g polyvinylpyrrolidone (PVP, molecular weight calculates by 29000) are successively dissolved in 80mL deionized water, after fully dissolving, are 100mL by this solution constant volume; 2. take 0.0227g NaBH 4be dissolved in 10mL deionized water; 3. the silver nitrate weak solution 25mL preparing in getting 1., adds the loaded catalyst Co of the three-dimensional ordered macroporous structure preparing 3o 4/ Eu 0.6sr 0.4feO 30.20g, the NaBH that concussion disperses to add after 3min 1.0mL to prepare in 2. 4solution, and be transferred to rapidly rotation stirring 60min on Rotary Evaporators, react rear slow filtration, and washed by 5.0ml deionized water, be at room temperature dried, obtain the composite catalyst Co of load monocrystalline Ag nanometer sheet 3o 4/ Eu 0.6sr 0.4feO 3.The wherein out-of-shape of monocrystalline Ag nanometer sheet, size heterogeneity, the silver strip (being about 50nm) that diameter is less is attached on carrier hole wall, and the silver strip that diameter is larger is distributed in carrier surface, observe silver strip thickness by TEM photo and be about 3 ~ 5 nanometers, there is the diffraction pattern of obvious Ag monocrystalline.In toluene conversion, lower than 30% time, this catalyst makes toluene conversion improve nearly 12% than raw catalyst.
Embodiment 2: step is 1. with 2. with embodiment 2; 3. the silver nitrate weak solution 25mL preparing in getting 1., adding 0.25mL mass fraction is 30% hydrogen peroxide, adds the loaded catalyst Co of the three-dimensional ordered macroporous structure preparing after mixing 3o 4/ Eu 0.6sr 0.4feO 30.20g, continues the NaBH that concussion disperses to add after 3min 1.0mL to prepare in 2. 4solution, and be transferred to rapidly rotation stirring 30min on Rotary Evaporators, react rear slow filtration, and washed by 5.0ml deionized water, be at room temperature dried, obtain the composite catalyst Co of load monocrystalline Ag nanometer sheet 3o 4/ Eu 0.6sr 0.4feO 3.The wherein out-of-shape of monocrystalline Ag nanometer sheet, size is heterogeneity also, is mainly distributed between carrier, presents the diffraction pattern of obvious Ag monocrystalline.In toluene conversion, lower than 20% time, this catalyst makes toluene conversion improve approximately 6% than raw catalyst.

Claims (2)

1. the monocrystalline Ag nanometer sheet/Co of three-dimensional ordered macroporous structure 3o 4/ Eu 0.6sr 0.4feO 3the preparation method of composite catalyst, the Ag nanometer sheet of load is monocrystalline, at Co 3o 4/ Eu 0.6sr 0.4feO 3in surface and duct, all load has monocrystalline Ag nanometer sheet, Co 3o 4/ Eu 0.6sr 0.4feO 3monocrystalline Ag nanometer sheet in duct is less than Co 3o 4/ Eu 0.6sr 0.4feO 3the monocrystalline Ag nanometer sheet on surface; It is characterized in that, comprise the following steps: 1. by AgNO 3, citric acid, PVP mol ratio be that 1:15:0.7 compound concentration is the AgNO of 0.4mmol/L 3solution, and the compound concentration NaBH that is 6.0mmol/L 4solution; 2. according to the demand of the percentage composition of loaded Ag on carrier, by 3DOM Co 3o 4/ Eu 0.6sr 0.4feO 3be immersed in above-mentioned AgNO 3in solution, after complete wetting, by AgNO 3with NaBH 4mol ratio is the above-mentioned NaBH that 1:6 gets certain volume 4solution joins this AgNO 3in solution, shake while be transferred to rapidly on Rotary Evaporators, 60min is stirred in room temperature rotation; 3. reacted rear slow filtration, and the material obtaining has been washed by deionized water, drying at room temperature, obtains the monocrystalline Ag nanometer sheet/Co of three-dimensional ordered macroporous structure 3o 4/ Eu 0.6sr 0.4feO 3composite catalyst, wherein the load capacity 1wt%-5wt% of monocrystalline Ag nanometer sheet.
2. according to the method for claim 1, it is characterized in that, the 2. step add a certain amount of 30wt.% hydrogen peroxide, by 1ml AgNO 3solution adds 0.01mL30wt.% hydrogen peroxide, and this reaction time is 30min, and other step is identical.
CN201210212461.6A 2012-06-21 2012-06-21 Single crystal Ag nanoplate/Co3O4/Eu0.6Sr0.4FeO3 composite catalyst, preparation thereof and application thereof Expired - Fee Related CN102728388B (en)

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