CN103301850B - Three-dimensional sequential macroporous Co3O4 loaded nanometer Au catalyst as well as preparation method and application thereof - Google Patents

Three-dimensional sequential macroporous Co3O4 loaded nanometer Au catalyst as well as preparation method and application thereof Download PDF

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CN103301850B
CN103301850B CN201310208233.6A CN201310208233A CN103301850B CN 103301850 B CN103301850 B CN 103301850B CN 201310208233 A CN201310208233 A CN 201310208233A CN 103301850 B CN103301850 B CN 103301850B
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3dom
catalyst
room temperature
co3o4
preparation
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CN103301850A (en
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戴洪兴
谢少华
邓积光
姜洋
韩文
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Beijing University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to a three-dimensional sequential macroporous Co3O4 loaded nanometer Au catalyst as well as a preparation method and an application thereof, and belongs to a transition metal oxide loaded nanometer noble metal catalyst. The pore wall of Co3O4 with a 3DOM structure is supported with cubic phase Au nanometer particles. According to the preparation method, 3DOM Co3O4 is prepared by a polyethyleneglycol 400 assisted PMMA (polymethyl methacrylate) colloidal crystal template method, and then a gold nanometer adhesive is loaded on 3DOM Co3O4 by using a polyvinyl alcohol protection bubble reduction method, so that Au/3DOM Co3O4 is obtained. The raw materials of the three-dimensional sequential macroporous Co3O4 loaded nanometer Au catalyst is cheap in price and can be easily obtained, the preparation process is simple, and the product obtained by the preparation method is controllable in shape, size and pore diameter.

Description

Three-dimensional ordered macroporous Co 3o 4loaded with nano Au catalyst, preparation method and application
Technical field
The present invention relates to a kind of Co adopting the bubbling reducing process of colloid crystal templating and polyvinyl alcohol protection to prepare three-dimensional ordered macroporous (3DOM) structure respectively 3o 4and gold-supported (Au/3DOM Co 3o 4) preparation method of catalyst, and the catalytic performance to CO and volatile organic matter oxidation, relate in particular to the Co adopting the bubbling reducing process of polymethyl methacrylate (PMMA) colloid crystal templating and polyvinyl alcohol protection to prepare 3DOM structure respectively 3o 4with Au/3DOM Co 3o 4the preparation method of catalyst, and the catalytic performance to CO and toluene oxidation, belong to transition metal oxide nano-noble-metal-loaded catalyst.
Background technology
Industrial waste gas [as volatile organic matter (VOCs) etc.] pollutant atmosphere, harm health of human body.Production by Catalytic Combustion Process is one of technology of removal VOCs the most frequently used at present, and by catalytic action, VOCs can be oxidized under lower temperature (<500 DEG C), and its clearance is usually above 95%.The selection of catalyst is crucial.The catalyst being applied to VOCs catalytic combustion at present comprises carried noble metal, single transition metal oxide and composite metal oxide.In the catalyst studied, the catalytic activity of supported precious metal catalyst to CO and VOCs oxidation reaction is best, the catalytic activity that wherein Au nanocatalyst is excellent to CO and VOCs oxidation display.Au is carried on the transition metal oxide (MO of high-specific surface area y) on carrier, also can improve its catalytic performance to CO and VOCs oxidation further.Such as: Yu etc. (X.H.Yu, et al., The Journal of Physical Chemistry C, 2012,116:851-860) observe Pt/MnO 2the good catalytic activity of catalyst oxidation of formaldehyde reaction and display.Jin etc. (M.S.Jin, et al., Catalysis Today, 2012,185:183-190) have prepared meso-pore Ce O 2and Mn 2o 3the palladium catalyst of load, finds Pd/ meso-pore Ce O 2the highest catalytic activity is demonstrated to CO oxidation reaction.Sinha etc. (A.K.Sinha, et al., Angewandte Chemie International Edition, 2007,46:2891-2894) have studied toluene, acetaldehyde and n-hexane at Au/ γ-MnO 2oxidation reaction on catalyst, finds that it shows good catalytic performance.Xue etc. (W.J.Xue, et al., Catalysis Communication, 2011,12:1265 – 1268) are at different-shape Co 3o 4upper load Au, find that the carrier of different-shape is very large to the activity influence of catalyst, this is due to different-shape Co 3o 4the active crystal face exposed is different and cause different from the degree of strength of Au nano particle effect.Solsona etc. (B.Solsona, et al., Journal of Hazardous Materials, 2011,187:544 – 552) have studied at Co 3o 4upper load Au nano particle, to toluene, propane and CO oxidation reaction, finds that it shows excellent catalytic performance, this is because can improve Co significantly after load Au particle 3o 4reducing power, there is strong interaction between Au and carrier, significantly improve Au 1+concentration.
Three-dimensional ordered macroporous (3DOM) structure catalyst because of have higher specific area, larger pore volume and prosperity pore structure and make it have very large application prospect in a lot of fields.Macroporous structure is conducive to reducing resistance to mass tranfer and impelling guest molecule to arrive active sites, thus is conducive to the absorption and diffusion of reactant molecule.In in the past 10 years, Chinese scholars has carried out inquiring into widely to the preparation of 3DOM material.People utilize recently set up be hard template with Colloidal crystals [as polymethyl methacrylate (PMMA) and polystyrene (PS) etc.)] micron ball the brilliant synthetic technology of glue can obtain the 3DOM material of aperture in tens of extremely hundreds of nanometer.Such as: Stein and partner (A.Stein, et al., Chemistry of Materials, 2000,12:1134-1141) thereof for template, with metal acetate salt or oxalates for predecessor, have synthesized the Fe of 3DOM structure with PS microballoon 2o 3, Cr 2o 3, Mn 2o 3and Co 3o 4, aperture is 380-550nm and specific area is 20-39m 2/ g.Ueda and partner (W.Ueda, et al., Chemistry of Materials, 2007,19:5779-5785) utilizes the PMMA microsphere of different-diameter to make template and metal nitrate is predecessor, has synthesized the Fe of 3DOM structure 2o 3, Cr 2o 3, Mn 2o 3, Mn 3o 4and Co 3o 4, aperture is 170-180nm and specific area is 13-57m 2/ g.
Co 3o 4the catalysis material with excellent activity, if it is made 3DOM Co 3o 4, then greatly can improve its specific area, improve surface and body phase character and be conducive to the diffusion of reactant molecule and activate absorption, thus improve its catalytic activity significantly; If more appropriate Au nano particle is supported 3DOM Co 3o 4on carrier, then can improve catalytic performance further.3DOM Co 3o 4in Co ion contain multiple oxidation state, there is stronger oxidationreduction (Redox) ability, Co 3o 4and strong interaction and synergy may be there is between Au, be conducive to the Redox process of promoting catalyst, thus be conducive to the raising of catalytic activity.Up to now, there is no document and patent report to cross the bubbling reducing process using colloid crystal templating protect in conjunction with polyvinyl alcohol and prepare the transition metal oxide supported precious metal catalyst Au/3DOM Co with 3DOM structure 3o 4.Therefore, research and development preparation has the Co of 3DOM structure 3o 4carried noble metal nanometer Au catalysis material is significant.
Summary of the invention
The object of the present invention is to provide 3DOM Co 3o 4pMMA colloid crystal templating and Au/3DOM Co 3o 4polyvinyl alcohol protection bubbling reducing process.
Three-dimensional ordered macroporous Co 3o 4loaded with nano Au catalyst, i.e. Au/3DOM Co 3o 4catalyst, is characterized in that, has the Co of 3DOM structure 3o 4hole wall on load have Emission in Cubic Au nano particle.
3DOM Co 3o 4with Au/3DOM Co 3o 4preparation method, it is characterized in that, adopt the bubbling reducing process of the PEG400 PMMA colloid crystal templating of assisting and polyvinyl alcohol protection to prepare 3DOM Co respectively 3o 4with Au/3DOM Co 3o 4, specifically comprise the following steps:
(1) 3DOM Co is prepared 3o 4: get cobalt nitrate hexahydrate and join in absolute methanol and stir 10min, obtain precursor liquid, PEG400 is added to mixing in precursor liquid, wherein cobalt nitrate hexahydrate: absolute methanol: PEG400 is 20mmol:9ml:1ml, after stirring at room temperature 30min, then add PMMA hard template, in room temperature immersion 3h, filtration, drying at room temperature 24h, namely obtain 3DOM Co after roasting 3o 4carrier, calcination steps and condition are: (a) is at N 2under atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, and keep 3h, be naturally down to room temperature subsequently; (b) in air atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, keep 2h, rise to 450 DEG C with 1 DEG C/min speed subsequently, keep naturally being down to room temperature after 3h;
(2) Au/3DOM Co is prepared 3o 4: ice-water bath light protected environment: joined by aqueous solution of chloraurate in the aqueous solution of PVA, Au/PVA mass ratio=1.5:1, uniform stirring 10min, adds NaBH rapidly subsequently 4water solution A u/NaBH 4mol ratio=1:5, after stirring 30min, i.e. obtained Au nanometre glue;
The bubbling reducing process of PVA protection and infusion process is adopted to prepare xAu/3DOM Co 3o 4catalyst: according to Au/3DOM Co 3o 4the Au load capacity estimated in catalyst, adds the 3DOM Co of preparation in step (1) in Au nanometre glue 3o 4carrier, adsorbs under gas sparging is auxiliary, after glue clarification (namely absorption completely), filter, washing and at 110 DEG C dry 12h, i.e. obtained Au/3DOM Co 3o 4catalyst.
Au/3DOM Co 3o 4middle Au load factor be x (as x=2,4,6,8%), as prepare the Au nano particle of different quality colloidal sol in add 200mg 3DOM Co 3o 4carrier, obtains the xAu/3DOM Co that actual Au load capacity is followed successively by 1.1,2.7,5.2 and 6.5% 3o 4catalyst.
The present invention has cheaper starting materials and is easy to get, and preparation process is simple, the features such as products therefrom pattern, particle diameter and aperture are controlled.
Au/3DOM Co prepared by the present invention 3o 4(x=1-8%) there is the feature of 3DOM structure and excellent catalytic activity, have a good application prospect in CO and VOCs catalytic oxidation field.
Utilize the crystal structure of the instrumental characterizing gained target products such as D8 ADVANCE type X-ray diffractometer (XRD), ZEISS SUPRA55 type SEM (SEM), JEOL-2010 type transmission electron microscope (TEM), particle morphology and pore structure, utilize inductively coupled plasma atomic emission spectrum (ICP-AES) to measure Au actual negative carrying capacity.Result shows, according to the xAu/3DOM Co obtained by the inventive method 3o 4(x=1-8%) catalyst presents 3DOM structure and uniform load has Emission in Cubic Au nano particle on large hole wall, and Au nanometer particle size is between 2.4-3.7nm.
Accompanying drawing explanation
Fig. 1 is obtained xAu/3DOM Co 3o 4(x=1.1,2.7,5.2,6.5%) XRD spectra of catalyst, wherein curve (a), (b), (c), (d) are respectively the XRD spectra of embodiment 1, embodiment 2, embodiment 3, embodiment 4 catalyst.
Fig. 2 is obtained xAu/3DOM Co 3o 4(x=1.1,2.7,5.2,6.5%) the SEM photo of catalyst, wherein figure (a) and (b), (c) and (d), (e) and (f), (g) and (h) are respectively the SEM photo of embodiment 1, embodiment 2, embodiment 3, embodiment 4 catalyst.
Fig. 3 is obtained xAu/3DOM Co 3o 4(x=1.1,2.7,5.2,6.5%) the HRTEM photo of catalyst, wherein figure (a), (b), (c) are respectively the TEM photo under the different amplification of embodiment 1, embodiment 2, embodiment 3, embodiment 4 catalyst with (d).
Fig. 4 is obtained xAu/3DOM Co 3o 4(x=1.1,2.7,5.2,6.5%) catalyst is through the Au nanometer particle size distribution map of HRTEM figure statistics, wherein schemes (a), (b), Au nanometer particle size distribution map that (c) and (d) are respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 catalyst.
Fig. 5 is obtained xAu/3DOM Co 3o 4(x=1.1,2.7,5.2,6.5%) catalytic activity of catalyst, wherein scheme (a), (b), (c) and (d) be respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 catalyst CO concentration to be 100ppm, CO and oxygen molar ratio be 1/20 and air speed be 10000mL/ (gh) condition under CO oxidation activity curve.
Fig. 6 is obtained xAu/3DOM Co 3o 4(x=1.1,2.7,5.2,6.5%) catalytic activity of catalyst, wherein scheme (a), (b), (c) and (d) be respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 catalyst toluene concentration to be 1000ppm, toluene and oxygen molar ratio be 1/400 and air speed be 40000mL/ (g h) condition under toluene oxidation activity curve.
Detailed description of the invention
Embodiment 1:
(1) get 20mmol cobalt nitrate hexahydrate to join in 9mL absolute methanol and stir 10min, 1mL PEG400 is added to mixing in precursor liquid, after stirring at room temperature 30min, add appropriate PMMA hard template again, in room temperature immersion 3h, filtration, drying at room temperature 24h, namely obtain 3DOM Co after roasting 3o 4carrier.Roasting condition is: (1) is at N 2under atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, and keep 3h, be naturally down to room temperature subsequently; (2) in air atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, keep 2h, rise to 450 DEG C with 1 DEG C/min speed subsequently, keep naturally being down to room temperature after 3h.
(2) ice-water bath light protected environment: get 13.54mL aqueous solution of chloraurate (1.5mmol/L) and join (Au/PVA mass ratio=1.5:1) in the aqueous solution (2.0mg/mL) of 1.33mL PVA, uniform stirring 10min, adds 1.92mL NaBH subsequently fast 4the aqueous solution (2.0mg/mL) (Au/NaBH 4mol ratio=1:5), Au nanometre glue is formed when solution becomes brownish black, stand-by after rapid stirring 30min.
(3) in (2) obtained Au nanometre glue, 200mg3DOM Co is added 3o 4carrier, at N 2adsorb under gas sparging is auxiliary, after glue clarification (namely absorption completely), filter, washing and at 110 DEG C dry 12h, i.e. obtained 1.1Au/3DOM Co 3o 4catalyst, aperture is about 290nm, and Au nano particle average grain diameter is 2.4nm.
Embodiment 2:
(1) get 20mmol cobalt nitrate hexahydrate to join in 9mL absolute methanol and stir 10min, 1mL PEG400 is added to mixing in precursor liquid, after stirring at room temperature 30min, add appropriate PMMA hard template again, in room temperature immersion 3h, filtration, drying at room temperature 24h, namely obtain 3DOM Co after roasting 3o 4carrier.Roasting condition is: (1) is at N 2under atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, and keep 3h, be naturally down to room temperature subsequently; (2) in air atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, keep 2h, rise to 450 DEG C with 1 DEG C/min speed subsequently, keep naturally being down to room temperature after 3h.
(2) ice-water bath light protected environment: get 27.08mL aqueous solution of chloraurate (1.5mmol/L) and join (Au/PVA mass ratio=1.5:1) in the aqueous solution (2.0mg/mL) of 2.67mL PVA, uniform stirring 10min, adds 3.84mL NaBH subsequently fast 4the aqueous solution (2.0mg/mL) (Au/NaBH 4mol ratio=1:5), Au nanometre glue is formed when solution becomes brownish black, stand-by after rapid stirring 30min.
(3) in (2) obtained Au nanometre glue, 200mg 3DOM Co is added 3o 4carrier, at N 2adsorb under gas sparging is auxiliary, after glue clarification (namely absorption completely), filter, washing and at 110 DEG C dry 12h, i.e. obtained 2.7Au/3DOM Co 3o 4catalyst, aperture is about 260nm, and Au nano particle average grain diameter is 2.6nm.
Embodiment 3:
(1) get 20mmol cobalt nitrate hexahydrate to join in 9mL absolute methanol and stir 10min, 1mL PEG400 is added to mixing in precursor liquid, after stirring at room temperature 30min, add appropriate PMMA hard template again, in room temperature immersion 3h, filtration, drying at room temperature 24h, namely obtain 3DOM Co after roasting 3o 4carrier.Roasting condition is: (1) is at N 2under atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, and keep 3h, be naturally down to room temperature subsequently; (2) in air atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, keep 2h, rise to 450 DEG C with 1 DEG C/min speed subsequently, keep naturally being down to room temperature after 3h.
(2) ice-water bath light protected environment: get 40.62mL aqueous solution of chloraurate (1.5mmol/L) and join (Au/PVA mass ratio=1.5:1) in the aqueous solution (2.0mg/mL) of 4.00mL PVA, uniform stirring 10min, adds 5.76mL NaBH subsequently fast 4the aqueous solution (2.0mg/mL) (Au/NaBH 4mol ratio=1:5), Au nanometre glue is formed when solution becomes brownish black, stand-by after rapid stirring 30min.
(3) in (2) obtained Au nanometre glue, 200mg 3DOM Co is added 3o 4carrier, at N 2adsorb under gas sparging is auxiliary, after glue clarification (namely absorption completely), filter, washing and at 110 DEG C dry 12h, i.e. obtained 5.2Au/3DOM Co 3o 4catalyst, aperture is about 280nm, and Au nano particle average grain diameter is 2.9nm.
Embodiment 4:
(1) get 20mmol cobalt nitrate hexahydrate to join in 9mL absolute methanol and stir 10min, 1mL PEG400 is added to mixing in precursor liquid, after stirring at room temperature 30min, add appropriate PMMA hard template again, in room temperature immersion 3h, filtration, drying at room temperature 24h, namely obtain 3DOM Co after roasting 3o 4carrier.Roasting condition is: (1) is at N 2under atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, and keep 3h, be naturally down to room temperature subsequently; (2) in air atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, keep 2h, rise to 450 DEG C with 1 DEG C/min speed subsequently, keep naturally being down to room temperature after 3h.
(2) ice-water bath light protected environment: get 54.16mL aqueous solution of chloraurate (1.5mmol/L) and join (Au/PVA mass ratio=1.5:1) in the aqueous solution (2.0mg/mL) of 5.33mL PVA, uniform stirring 10min, adds 7.68mL NaBH subsequently fast 4the aqueous solution (2.0mg/mL) (Au/NaBH 4mol ratio=1:5), Au nanometre glue is formed when solution becomes brownish black, stand-by after rapid stirring 30min.
(3) in (2) obtained Au nanometre glue, 200mg 3DOM Co is added 3o 4carrier, at N 2adsorb under gas sparging is auxiliary, after glue clarification (namely absorption completely), filter, washing and at 110 DEG C dry 12h, i.e. obtained 6.5Au/3DOM Co 3o 4catalyst, aperture is about 270nm, and Au nano particle average grain diameter is 3.7nm.
Resulting material of the present invention is novel, particle morphology and hole dimension controlled, there is good catalytic activity.In CO concentration, to be 100ppm, CO and oxygen molar ratio be 1/20 and under air speed is 10000mL/ (g h) condition, 6.5Au/3DOM Co 3o 4temperature when toluene conversion reaches 10%, 50% and 100% on catalyst is respectively-68 DEG C ,-42 DEG C and-30 DEG C.In toluene concentration, to be 1000ppm, toluene and oxygen molar ratio be 1/400 and under air speed is 40000mL/ (g h) condition, 7.5Au/3DOM Mn 2o 3temperature when toluene conversion reaches 10%, 50% and 90% on catalyst is respectively 215 DEG C, 244 DEG C and 256 DEG C.

Claims (3)

1. prepare three-dimensional ordered macroporous Co 3o 4the method of loaded with nano Au catalyst, three-dimensional ordered macroporous Co 3o 4loaded with nano Au catalyst, has the Co of 3DOM structure 3o 4hole wall on load have Emission in Cubic Au nano particle, it is characterized in that, adopt the bubbling reducing process of the PEG400 PMMA colloid crystal templating of assisting and polyvinyl alcohol protection to prepare 3DOM Co respectively 3o 4with Au/3DOM Co 3o 4, specifically comprise the following steps:
(1) 3DOM Co is prepared 3o 4: get cobalt nitrate hexahydrate and join in absolute methanol and stir 10min, obtain precursor liquid, PEG400 is added to mixing in precursor liquid, wherein cobalt nitrate hexahydrate: absolute methanol: PEG400 is 20mmol:9ml:1ml, after stirring at room temperature 30min, then add PMMA hard template, in room temperature immersion 3h, filtration, drying at room temperature 24h, namely obtain 3DOM Co after roasting 3o 4carrier, calcination steps and condition are: (a) is at N 2under atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, and keep 3h, be naturally down to room temperature subsequently; (b) in air atmosphere with 1 DEG C/min speed by room temperature to 300 DEG C, keep 2h, rise to 450 DEG C with 1 DEG C/min speed subsequently, keep naturally being down to room temperature after 3h;
(2) Au/3DOM Co is prepared 3o 4: ice-water bath light protected environment: joined by aqueous solution of chloraurate in the aqueous solution of PVA, Au/PVA mass ratio=1.5:1, uniform stirring 10min, adds NaBH rapidly subsequently 4water solution A u/NaBH 4mol ratio=1:5, after stirring 30min, i.e. obtained Au nanometre glue;
The bubbling reducing process of PVA protection and infusion process is adopted to prepare xAu/3DOM Co 3o 4catalyst: according to Au/3DOM Co 3o 4the Au load capacity estimated in catalyst, adds the 3DOM Co of preparation in step (1) in Au nanometre glue 3o 4carrier, adsorbs under gas sparging is auxiliary, after glue clarification (namely absorption completely), filter, washing and at 110 DEG C dry 12h, i.e. obtained Au/3DOM Co 3o 4catalyst.
2. according to the method for claim 1, it is characterized in that, Au load factor is 1-8%.
3. according to three-dimensional ordered macroporous Co prepared by the method for claim 1 3o 4loaded with nano Au catalyst is used for the catalytic oxidation of CO and toluene.
CN201310208233.6A 2013-05-30 2013-05-30 Three-dimensional sequential macroporous Co3O4 loaded nanometer Au catalyst as well as preparation method and application thereof Expired - Fee Related CN103301850B (en)

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104841453B (en) * 2015-04-10 2018-01-12 北京工业大学 Three-dimensional ordered macroporous Au Pd CoO/MOXCatalyst, preparation method and application
CN105126918B (en) * 2015-09-28 2017-06-23 云南大学 The large pore spherical composite catalyst and preparation method of removal benzene in air system thing
CN106391045B (en) * 2016-08-29 2019-04-09 浙江工业大学 A kind of preparation and use of the loaded noble metal catalyst based on cobaltosic oxide array
CN108452797B (en) * 2017-02-17 2021-01-05 中国科学院上海高等研究院 Metal oxide loaded noble metal catalyst, preparation method and application
CN108311147A (en) * 2018-01-24 2018-07-24 北京科技大学 Preparation method for the perovskite supported noble metal catalyst for purifying benzene
CN109847761A (en) * 2019-01-11 2019-06-07 山东师范大学 A kind of Co3O4@Au nano catalytic composite materials and preparation method thereof
CN109821552A (en) * 2019-03-06 2019-05-31 北京工业大学 Two-dimensional ultrathin Co3O4Load NanoPt catalyst, preparation method and application
CN112547059B (en) * 2020-09-07 2024-01-26 北京工业大学 Ru/3DOM SnO with good stability 2 Preparation method and application of catalyst

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2037519A1 (en) * 2006-06-13 2009-03-18 Toyota Jidosha Kabushiki Kaisha Fine particle of perovskite oxide, particle having deposited perovskite oxide, catalyst material, catalyst material for oxygen reduction, catalyst material for fuel cell, and electrode for fuel cell
CN102728388A (en) * 2012-06-21 2012-10-17 北京工业大学 Single crystal Ag nanoplate/Co3O4/Eu0.6Sr0.4FeO3 composite catalyst, preparation thereof and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2037519A1 (en) * 2006-06-13 2009-03-18 Toyota Jidosha Kabushiki Kaisha Fine particle of perovskite oxide, particle having deposited perovskite oxide, catalyst material, catalyst material for oxygen reduction, catalyst material for fuel cell, and electrode for fuel cell
CN102728388A (en) * 2012-06-21 2012-10-17 北京工业大学 Single crystal Ag nanoplate/Co3O4/Eu0.6Sr0.4FeO3 composite catalyst, preparation thereof and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Au/3DOM LaCoO3:High-performance catalysts for the oxidation of carbon monoxide and toluene;Xinwei Li等;《Chemical Engineering Journal》;20130529;第228卷;第966页2.1 *
Lysine-aided PMMA-templating preparation and high performance of three-dimensionally ordered macroporous LaMnO3 with mesoporous walls for the catalytic combustion of toluene;YuXi Liu等;《Applied Catalysis B: Environmental》;20120217;第119-120卷;第20-31页 *
Mesoporous Co3O4 and Au/Co3O4 Catalysts for Low-Temperature Oxidation of Trace Ethylene;Chun Yan Ma等;《J.AM.CHEM.SOC.》;20100208;第132卷;第2608页摘要；第2610页图2；第2611页2.2；第2609页左栏第3段 *

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