CN102580744A - Multi-stage cobalt ferrite oxide nano array structured catalyst and preparation method thereof - Google Patents
Multi-stage cobalt ferrite oxide nano array structured catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a multi-stage cobalt ferrite oxide nano array structured catalyst and a preparation method thereof, belonging to the technical field of catalysis. The catalyst is a cobalt ferrite oxide film micron sheet which is directly grown on a ferrum substrate, has a large-scale high-activity {112} crystal plane and has sheet-like morphology formed by weaving nanowires, wherein nano-scale cobalt ferrite oxide nanowires are also grown on the cobalt ferrite oxide film micron sheet; and the chemical general formula of the cobalt ferrite oxide is Co<3-x>FexO4 and x is more than 0 and not more than 2. The preparation method is characterized by growing the cobalt ferrite hydrotalcite micron sheet on the ferrum substrate by the in-situ hydrothermal synthesis technology, then epitaxially growing the ferrum substituted basic cobaltous carbonate nanowires on the hydrotalcite sheet and finally obtaining the structured catalyst through high temperature roasting. The structured catalyst can be used in catalytic oxidation reaction of styrene, has high reactant conversion rate and product selectivity and can also solve a series of problems caused by homogeneous catalysts and bulk particle catalysts to ensure the process to meet the requirements of environment friendliness and sustainable development.
Description
Technical field
The invention belongs to catalysis technical field, it is suprabasil structurally ordered to be specifically related to be grown in iron, preferentially exposes the high activity crystal face, the multistage cobalt iron oxide nano array structure Catalysts and its preparation method of even size distribution.
Background technology
Along with the problem of scarcity of resources, ecological deterioration is increasingly serious, the green chemical industry process of energy-saving and emission-reduction consumption reduction becomes chemical field researcher institute pursuing target.Catalyst material, as the core in the chemical reaction process, its development and utilization is concerning the development and the technological progress in fields such as the energy, environment and resource.Heterogeneous catalyst, uses in industry owing to can separate through better simply phase disengagement method and product as one type of solid catalyst in a large number.The at present heap beaded catalysts that loose that adopt of industrial heterogeneous catalyst exist high pressure drop, shortcomings such as high abrasion more.Beaded catalyst looses and to pile in bed, the flow channel out-of-shape that the particle gap forms, and pressure fell greatlyyer when fluid was flowed through fixed bed, and kinetic energy consumes high.The beaded catalyst size is less, moves with fluid easily, if mechanical strength own is relatively poor, then can stop up because of mutual frictional impact generation breaking and Dusting causes the air-flow duct, and pressure drop increases, aggravation high pressure drop, high energy consumption phenomenon.One of effective way that the Structured Design of heterogeneous catalysis agent material is considered to address this problem.Structural catalyst is because architectural feature that regular carrier had, characteristics such as the catalytic reaction bed that its is formed has that the fluid that is different from conventional granulates type catalyst reaction bed flows, mass transfer and heat transfer.It provides even, regular, straight-through duct, and has big voidage.The path that fluid is flowed through therein is seldom having many bends or curves, can under the different fluids dynamics state, operate.The regular texture of structural catalyst helps material and fully contacts with the even of catalyst.Simultaneously, this also reduces or has been avoided because the heat spot of the inhomogeneous generation of flowing.In addition, the amplification of structural catalyst can be thought simple and clear, because the condition in the independent duct is constant.Different with conventional fixed bed reactors, the thickness of structuring catalyst reactor coating can be very little, and diffusion length is short in the regular catalyst layer, helps eliminating the influence of inside diffusional resistance to heterogeneous reaction, and catalyst utilization is very high.But the preparation process of structural catalyst generally includes the preparation of carrier now; Three steps of the preparation of coating and the load of active component; Like this because the particularity of structure usually causes the active component skewness; Not strong with the caking property of carrier, directly influence its catalytic performance and use.The design of therefore novel structural catalyst with become one of present problem demanding prompt solution.In recent years, the development of nano material controlledly synthesis technology and the progress of analysis means were for the exploitation of high performance catalyst brought new opportunity.The nano-array material is with the photoelectric characteristic and the catalysis characteristics of its novel structure, uniqueness, and the application in fields such as nano-device making has huge advantage and potentiality to receive people's very big concern.On the other hand, the miniaturization of catalyst material size has been proved to be to improve the effective way of catalytic performance, through increasing the touch opportunity of reaction of atomic such as surface and gas, liquid, activity is improved.For the nano-array of compound with regular structure, can increase the specific area of catalyst integral material through the size that reduces monodimension nanometer material; In addition, the pattern of material and crystal face effect have also caused people's extensive concern.For the well-crystallized and have for given shape nanocrystalline, its surface generally is made up of the crystal face of confirming.Because the activity that structure-sensitive is reflected on the different crystal faces of same substance often there are differences, thereby causes catalytic activity and selectivity to change.Therefore the catalytic performance that relevant with catalyst crystal face character surface texture and surface-active site have determined catalyst to a great extent.
Spinelle Co
3-xFe
xO
4Because it does not change spinelle lattice configuration in oxidation-reduction process, have good structural stability and catalytic performance, be a kind of effective catalyst therefore for a large amount of chemical reaction processes.Can be used for such as it: the decomposition of alcohols and hydrogen peroxide, the oxidation of CO (Xie, X.; Li, Y.; Liu, Z.-Q.; Haruta, M.; Shen, W.Nature 2009,458,746-749.), burning (Hu, the L. of saturated alkane; Peng, Q.; Li, Y. J.Am.Chem.Soc.2008,130,16136-16137.), oxidation (Guin, the D. of alkene; Baruwati, B.; Manorama, S.V., Journal of Molecular Catalysia A:Chemical 2005,242,26-31.), oxidation (Tong, the J. of cyclohexane; Bo, L.; Li, Z.; Lei, Z.; Xia, C., Journal of Molecular Catalysis A:Chemical 2009,307,58.).
But up to the present, the research work that is applied to structural catalyst for nano-array is also less, to a certain degree limit the commercial development and the application of high performance catalyst.We propose with the imagination of the structurally ordered nano-array with vast scale high activity crystal face preferred orientation as structural catalyst based on this; The nano-array that forms by catalytic active component; Since can be in substrate the direct growth catalytic active substance, the nanostructured of formation confirms, in order, can realize high specific area; Solve traditional integral catalyst activity component skewness, the problem not strong with the caking property of carrier.Here we have estimated multistage Co with cinnamic catalytic oxidation
3-xFe
xO
4The performance of nano array structure catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of multistage cobalt iron oxide nano array structure Catalysts and its preparation method.
A kind of multistage cobalt iron oxide nano array structure catalyst provided by the invention is to be grown directly upon that iron is suprabasil to have the vast scale high activity { nano wire of 112} crystal face is woven into the cobalt iron oxide film micron film of sheet pattern; The nano level cobalt iron oxide nano wire of also growing on the cobalt iron oxide film micron film, the chemical general formula of cobalt iron oxide is: Co
3-xFe
xO
4, 0＜x≤2 wherein.
The above-mentioned a kind of multistage cobalt iron oxide nano array structure Preparation of catalysts method of the present invention; Adopt the original position hydro-thermal synthetic technology ferro-cobalt hydrotalcite micron film of having grown at the bottom of the iron-based; Afterwards on hydrotalcite sheets epitaxial growth the substituted basic carbonate cobalt nanowire of iron; After high-temperature roasting obtains structurally ordered; Preferential expose high activity on the multilevel hierarchy that the nano wire of 112} crystal face is woven into the sheet pattern vertically is grown at the bottom of the iron-based in an orderly manner, the multistage cobalt iron oxide nano array structure catalyst of even size distribution, and be arranged in the Fe of octahedral position
3+Doping improved its catalytic activity.Concrete preparation method is following:
A. with 8-40cm
2Iron-based at the bottom of with hydrochloric acid (preferred 1mol/L) ultrasonic cleaning (preferred 5-10min), with absolute ethyl alcohol or acetone ultrasonic cleaning 5-10min, clean up with deionized water more again, obtain at the bottom of the iron-based subsequent use;
B. solubility cobalt salt, ammonium fluoride and urea are dissolved in wiring solution-forming in the deionized water, wherein the concentration of cobalt ions is 0.01-2mol/L, and ammonium fluoride is 1-4 with the amount of substance ratio of cobalt ions, and urea is 1-10 with the amount of substance ratio of cobalt ions;
C. with immersing step b gained mixed solution at the bottom of the step a gained iron-based, and in agitated reactor 60-200 ℃ of temperature hydro-thermal 4-48h, reaction naturally cools to room temperature after finishing; Gained substrate water and absolute ethanol washing remove impurity, dry 1-8h in 60-100 ℃ of baking oven;
D. with step c gained substrate 200-600 ℃ of roasting 1-8h in Muffle furnace, get final product multistage cobalt iron oxide nano array structure catalyst.
The solubility cobalt salt is cobalt nitrate, cobaltous sulfate, cobalt chloride among the step b, or above-mentioned hydrate.
With the above-mentioned multistage cobalt iron oxide nano array structure catalyst applications that makes in the catalytic oxidation of phenylethene synthesizing benzaldehyde.Reaction condition is 60-100 ℃ of reaction 8-16h down, adopts acetonitrile to make solvent, and solvent load is a 5-15mL/mL styrene, and oxidant TBHP consumption is a 1-2mL/mL styrene, and every milliliter of styrene adds the described structural catalyst 0.1g of steps d.
The invention has the advantages that: at the bottom of (1) iron-based direct growth have the vast scale high activity nano wire of 112} crystal face is woven into the multi-stage nano array structure catalyst of sheet pattern, the nanometer material structure of formation confirms, in order, can realize high specific area; (2) the suprabasil hydrotalcite micron film of iron is linking the substrate and the nano level nano wire of macroscopic scale, and this has guaranteed enough adhesive force and has been avoided the drop in catalytic reaction to go out.Simultaneously, micron film provides three-dimensional support to support Co
3-xFe
xO
4Growth, this provides large-area rough surface and has been avoided the gathering in the growth course.(3) micron film is that the epitaxial growth of multistage composite array provides template.Compare with traditional nano-wire array, the space on the micron film between the nano wire of vicinity is bigger, helps gas diffusion process, has caused the high usage of material; (4) Fe
3+Doping improved its catalytic activity; Based on above advantage, multistage cobalt iron oxide nano-array shows excellent catalytic performance.Prepared structural catalyst can effectively be used for the catalytic oxidation of phenylethene reaction, and reaction-ure conversion-age is high, and selectivity of product is high.It also can solve by homogeneous catalyst and a series of problems that the heap beaded catalyst that looses brings in addition, makes this technology satisfy the requirement of environmental protection and sustainable development.It can be effective to the catalytic oxidation of phenylethene synthesizing benzaldehyde, and cinnamic conversion ratio is 92.2%, and the selectivity of benzaldehyde is 64.6%.Compare multistage Co with the spinel catalyst of reporting before
3-xFe
xO
4Nano-array has outstanding stable circulation performance simultaneously, and recycling the back pattern through 9 times does not have to change basically, and the what is more important catalytic performance also remains unchanged basically.Solved traditional integral catalyst activity component skewness, not strong with the caking property of carrier, the active problem that progressively descends in the reaction.This multilevel hierarchy catalyst design strategy can be extended on metallic substrates synthetic other multilevel hierarchy metal oxide nano array, and new approaches is provided for the design of new and effective structural catalyst.
Description of drawings
Fig. 1 is the XRD figure of the prepared structural catalyst of embodiment 1;
Fig. 2 is the SEM figure of the prepared structural catalyst of embodiment 1;
Fig. 3 is the HRTEM figure of the prepared structural catalyst of embodiment 1;
Fig. 4 is the EDS figure of the prepared structural catalyst of embodiment 1;
Fig. 5 is the catalytic performance figure of the prepared structural catalyst of embodiment 1;
Fig. 6 is the repeat performance figure of the prepared structural catalyst of embodiment 1;
Fig. 7 is the SEM figure of the prepared structural catalyst of embodiment 2;
Fig. 8 is the SEM figure of the prepared structural catalyst of Comparative Examples.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1:
A. with 40cm
2Iron-based at the bottom of with hydrochloric acid (1mol/L) ultrasonic cleaning 5min, use absolute ethyl alcohol ultrasonic cleaning 5min again, clean up with deionized water again, obtain at the bottom of the iron-based subsequent use;
B. 5.8200g cabaltous nitrate hexahydrate, 2.9630g ammonium fluoride and 6.0000g urea are dissolved in the 400mL deionized water, after stirring, in the water heating kettle of packing into;
C. with immersing step b gained mixed solution at the bottom of the step a gained iron-based, and in agitated reactor 120 ℃ of temperature hydro-thermal 12h, reaction naturally cools to room temperature after finishing; Gained substrate water and absolute ethanol washing remove impurity, dry 2h in 80 ℃ of baking ovens;
D. the substrate of step c gained is placed on roasting in the Muffle furnace, rises to 400 ℃ of roasting 4h with the speed of 10 ℃/min by room temperature, roasting naturally cools to room temperature after accomplishing, get final product multistage Co
3-xFe
xO
4(x ≈ 1.2) nano array structure catalyst, the nano wire that is woven into the hexagon sheet becomes 60 ° of angles each other, and nano wire is about 10 microns, wide about 200 nanometers, high about 80 nanometers.
The XRD figure of prepared structural catalyst is seen Fig. 1, and SEM figure sees Fig. 2, and HRTEM figure sees Fig. 3, and EDS figure sees Fig. 4.
With the multistage cobalt iron oxide nano array structure catalyst applications that makes in the catalytic oxidation of phenylethene synthesizing benzaldehyde.Reaction condition is 80 ℃ of reaction 12h down, 1.14mL styrene, 10mL acetonitrile; Oxidant TBHP consumption is 1.56mL; Add the described structural catalyst 0.1g of steps d, gas chromatography analysis for sampling, cinnamic conversion ratio are 92.2%; The selectivity of benzaldehyde is 64.6%, and the selectivity of styrene oxide is 16.8%.
Catalytic performance figure sees that Fig. 5 (wherein also comprises and conventional nano wire Co
3O
4Comparable situation as catalyst), repeat performance figure sees Fig. 6.
Embodiment 2:
A. with 8cm
2Iron-based at the bottom of with hydrochloric acid (1mol/L) ultrasonic cleaning 5min, use absolute ethyl alcohol ultrasonic cleaning 5min again, clean up with deionized water again, obtain at the bottom of the iron-based subsequent use;
B. 9.312g cabaltous nitrate hexahydrate, 2.3704g ammonium fluoride and 9.6000g urea are dissolved in the 320mL deionized water, after stirring, in the water heating kettle of packing into;
C. with immersing step b gained mixed solution at the bottom of the step a gained iron-based, and in agitated reactor 120 ℃ of temperature hydro-thermal 24h, reaction naturally cools to room temperature after finishing; Gained substrate water and absolute ethanol washing remove impurity, dry 2h in 80 ℃ of baking ovens;
D. the substrate of step c gained is placed on roasting in the Muffle furnace, rises to 400 ℃ of roasting 4h with the speed of 10 ℃/min by room temperature, roasting naturally cools to room temperature after accomplishing, get final product multistage cobalt iron oxide nano array structure catalyst.
With the multistage cobalt iron oxide nano array structure catalyst applications that makes in the catalytic oxidation of phenylethene synthesizing benzaldehyde.Reaction condition is 80 ℃ of reaction 12h down, 1.14mL styrene, 10mL acetonitrile; Oxidant TBHP consumption is 1.56mL; Add the described structural catalyst 0.1g of steps d, gas chromatography analysis for sampling, cinnamic conversion ratio are 78%; The selectivity of benzaldehyde is 66%, and the selectivity of styrene oxide is 20.5%.
The SEM figure of prepared structural catalyst sees Fig. 7.
Comparative Examples:
A. with 10cm
2Iron-based at the bottom of with hydrochloric acid (1mol/L) ultrasonic cleaning 5min, use absolute ethyl alcohol ultrasonic cleaning 5min again, clean up with deionized water again, obtain at the bottom of the iron-based subsequent use;
B. 1.1640g cabaltous nitrate hexahydrate, 0.5926g ammonium fluoride and 1.2000g urea are dissolved in the 80mL deionized water, after stirring, in the water heating kettle of packing into;
C. with immersing step b gained mixed solution at the bottom of the step a gained iron-based, and in agitated reactor 120 ℃ of temperature hydro-thermal 3h, reaction naturally cools to room temperature after finishing; Gained substrate water and absolute ethanol washing remove impurity, dry 2h in 80 ℃ of baking ovens;
D. the substrate of step c gained is placed on roasting in the Muffle furnace, rises to 400 ℃ of roasting 4h with the speed of 10 ℃/min by room temperature, roasting naturally cools to room temperature after accomplishing, get final product multistage cobalt iron oxide nano array structure catalyst.
With the multistage cobalt iron oxide nano array structure catalyst applications that makes in the catalytic oxidation of phenylethene synthesizing benzaldehyde.Reaction condition is 80 ℃ of reaction 12h down, 1.14mL styrene, 10mL acetonitrile; Oxidant TBHP consumption is 1.56mL; Add the described structural catalyst 0.1g of steps d, gas chromatography analysis for sampling, cinnamic conversion ratio are 83.7%; The selectivity of benzaldehyde is 67.5%, and the selectivity of styrene oxide is 16.1%.
The SEM figure of prepared structural catalyst sees Fig. 8.
Claims (5)
1. multistage cobalt iron oxide nano array structure catalyst; It is characterized in that; Be to be grown directly upon that iron is suprabasil to have the vast scale high activity { nano wire of 112} crystal face is woven into the cobalt iron oxide film micron film of sheet pattern; The nano level cobalt iron oxide nano wire of also growing on the cobalt iron oxide film micron film, the chemical general formula of cobalt iron oxide is: Co
3-xFe
xO
4, 0＜x≤2 wherein.
2. the described a kind of multistage cobalt iron oxide nano array structure Preparation of catalysts method of claim 1 is characterized in that, comprises the steps:
A. with 8-40cm
2Iron-based at the bottom of clean with hydrochloric ultrasonic wave, with absolute ethyl alcohol or acetone ultrasonic cleaning 5-10min, clean up with deionized water more again, obtain at the bottom of the iron-based subsequent use;
B. solubility cobalt salt, ammonium fluoride and urea are dissolved in wiring solution-forming in the deionized water, wherein the concentration of cobalt ions is 0.01-2mol/L, and ammonium fluoride is 1-4 with the amount of substance ratio of cobalt ions, and urea is 1-10 with the amount of substance ratio of cobalt ions;
C. with immersing step b gained mixed solution at the bottom of the step a gained iron-based, and in agitated reactor 60-200 ℃ of temperature hydro-thermal 4-48h, reaction naturally cools to room temperature after finishing; Gained substrate water and absolute ethanol washing remove impurity, dry 1-8h in 60-100 ℃ of baking oven;
D. with step c gained substrate 200-600 ℃ of roasting 1-8h in Muffle furnace, get final product multistage cobalt iron oxide nano array structure catalyst.
3. according to the method for claim 2, it is characterized in that the solubility cobalt salt is cobalt nitrate, cobaltous sulfate, cobalt chloride among the step b, or above-mentioned hydrate.
4. the described a kind of multistage cobalt iron oxide nano array structure catalyst applications of claim 1 is in the catalytic oxidation of phenylethene synthesizing benzaldehyde.
5. according to the application of claim 4, it is characterized in that reaction condition is 60-100 ℃ of reaction 8-16h down; Adopt acetonitrile to make solvent; Solvent load is a 5-15mL/mL styrene, and oxidant TBHP consumption is a 1-2mL/mL styrene, and every milliliter of styrene adds structural catalyst 0.1g.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103316681A (en) * | 2013-07-19 | 2013-09-25 | 中国科学院山西煤炭化学研究所 | Nano-array structured catalyst used for Fischer-Tropsch synthesis and preparation method and application thereof |
| CN104841450A (en) * | 2015-04-14 | 2015-08-19 | 上海大学 | Preparation method of composite oxide entire denitration catalyst with three-dimensional graded core-shell structure |
| CN105280387A (en) * | 2015-11-21 | 2016-01-27 | 河南师范大学 | A sulfur and selenium compound composite array preparation method |
| CN107739058A (en) * | 2017-11-02 | 2018-02-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of self assembly rhombus flowers Co3O4 nanometer material and products thereof and application |
| CN109316920A (en) * | 2018-10-17 | 2019-02-12 | 厦门大学 | A kind of catalyst of transition metal oxide, preparation method and applications |
| CN110282663A (en) * | 2019-08-06 | 2019-09-27 | 厦门大学 | A method of different dimensions nano material is prepared based on same metal iron ion |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306986A (en) * | 2008-07-11 | 2008-11-19 | 湖南大学 | Process for preparing benzaldehyde by catalytic oxidation of phenylethene |
| CN101822981A (en) * | 2010-04-30 | 2010-09-08 | 北京化工大学 | Supported gold catalyst and preparation method thereof |
-
2012
- 2012-01-19 CN CN2012100172954A patent/CN102580744A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306986A (en) * | 2008-07-11 | 2008-11-19 | 湖南大学 | Process for preparing benzaldehyde by catalytic oxidation of phenylethene |
| CN101822981A (en) * | 2010-04-30 | 2010-09-08 | 北京化工大学 | Supported gold catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| J. JIANG 等: "General Synthesis of Large-Scale Arrays of One-Dimensional Nanostructured Co3O4 Directly on Heterogeneous Substrates", 《CRYSTAL GROWTH AND DESIGN》, vol. 10, 16 December 2009 (2009-12-16) * |
| JIAQIANG SUN等: "Hierarchical cobalt iron oxide nanoarrays as structured catalysts", 《CHEMICAL COMMUNICATIONS》, vol. 48, 10 January 2012 (2012-01-10) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103316681A (en) * | 2013-07-19 | 2013-09-25 | 中国科学院山西煤炭化学研究所 | Nano-array structured catalyst used for Fischer-Tropsch synthesis and preparation method and application thereof |
| CN103316681B (en) * | 2013-07-19 | 2015-06-17 | 中国科学院山西煤炭化学研究所 | Nano-array structured catalyst used for Fischer-Tropsch synthesis and preparation method and application thereof |
| CN104841450A (en) * | 2015-04-14 | 2015-08-19 | 上海大学 | Preparation method of composite oxide entire denitration catalyst with three-dimensional graded core-shell structure |
| CN105280387A (en) * | 2015-11-21 | 2016-01-27 | 河南师范大学 | A sulfur and selenium compound composite array preparation method |
| CN105280387B (en) * | 2015-11-21 | 2018-05-08 | 河南师范大学 | A kind of preparation method of sulphur selenium compound composite array |
| CN107739058A (en) * | 2017-11-02 | 2018-02-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of self assembly rhombus flowers Co3O4 nanometer material and products thereof and application |
| CN109316920A (en) * | 2018-10-17 | 2019-02-12 | 厦门大学 | A kind of catalyst of transition metal oxide, preparation method and applications |
| CN110282663A (en) * | 2019-08-06 | 2019-09-27 | 厦门大学 | A method of different dimensions nano material is prepared based on same metal iron ion |
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Application publication date: 20120718 |