CN103357891B - Preparation method and application of nickel and cobalt multi-level branching structure - Google Patents
Preparation method and application of nickel and cobalt multi-level branching structure Download PDFInfo
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Abstract
The invention provides a preparation method and an application of a nickel and cobalt multi-level branching structure. The nickel and cobalt multi-level branching structure can be applied in acetophenone and nitrobenzene catalytic hydrogenation reaction. The method for preparing nickle and cobalt comprises the following steps that a nickle precursor or a cobalt precursor is mixed with organic amine; H2 with certain pressure intensity is supplied; and a mixture is heated. The method can easily control the particle size and the shape of nano nickle and nano cobalt, and successfully synthesizes the nickel and cobalt multi-level branching structure. The multi-level branching nano nickle catalytic hydrogenation reaction is higher than catalytic hydrogenation reaction of nano nickle particles. A catalyst has better catalytic activity, and has a better industrial application prospect.
Description
Technical field
The present invention relates to the new pattern hydrogenation catalyst of a kind of racemosus shape, the preparation method of this catalyst and the application in acetophenone or By Catalytic Hydrogenation of Nitrobenzene reaction thereof.
Background technology
In recent years, the synthesis strategy utilizing nanosphere, nanometer rods or nanometer sheet to construct to have fractionation of complex structure has become one of investigation of materials field focus.Research finds, compared with single low-dimensional nano structure, the nano material with hierarchy often demonstrates more novel character, and it has reality or potential meaning in absorption, catalysis and sensor.W metal, metal Co are important magnetic functional materials, have excellent electricity, magnetic and catalytic performance and have extensive use in a lot of fields.As everyone knows, the factor height correlations such as the performance of nano material and the size of material, pattern and dimension thereof, therefore prepare shape anisotropy and there is the Ni particle of classification nanostructure, Co particle is one of focus of nanometer magnetic metal research.
Nickel nano material, due to the performance such as magnetic, light, photoelectricity, catalysis of uniqueness, has a wide range of applications in hydrogen storage material, photochemical catalyst, Magnetic Sensor, low temperature superplasticity, high density magnetic recording etc.The preparation of early stage people's many concerns nano nickel powder, achieves its application in fields such as carbide alloy bonding agent, catalyst and coating.In recent years, it is found that the pattern of nano nickel is very large on the impact of its characterisitic parameter, the especially successful preparation of 1-dimention nano nickel, makes its application performance further be expanded, as the hydrogen storage property of Nickel nanotubes array, and the exploitation etc. of magnetic recording instrument.At present, the synthetic method of nano nickel has: hydrothermal synthesis method, solvent-thermal process method, polyol process, and solid phase method (mechanochemical method, physical crushing method), vapor phase method etc.; Wherein, solvent-thermal method has the advantage of its uniqueness, and reactant has very high reactivity in organic solvent, can obtain interesting optics, the metastable phase of electricity and magnetic performance.
Nanometer cobalt is as a kind of important magnetic Nano material, and the size of nanometer cobalt and morphosis directly have influence on the performance of nanometer cobalt.Compared with nano cobalt granule, the nanometer cobalt of general shape anisotropy shows the performance of a series of excellence.At present, many researchers control to do a lot of work in synthesis at the pattern of cobalt granule, and they use polyol process, induced by magnetic field method or microemulsion method etc. have synthesized the nanometer cobalt of a series of different structure, as cobalt nanorod, and chain nanometer cobalt, flower-like nanometer cobalt, cobalt nanowire etc.
Aromatic alcohol is the important chemical products of a class, at spices, has a wide range of applications in medicine and other fine chemical products.1-benzyl carbinol is compound representative in aromatic alcohol, is also a kind of important chemical products, is widely used in perfume synthesis, the synthesis of essential oil, and in a lot of pharmaceutical synthesis, benzyl carbinol is important pharmaceutical intermediate.In all multi-routes of synthesis benzyl carbinol, prepare benzyl carbinol from acetophenone catalytic hydrogenation and be subject to extensive concern because meeting Atom economy most.Acetophenone is the better simply aromatic ketone of structure and containing chiral carbonyl of diving, hydrogenation products has benzyl carbinol, the ethylbenzene after 1-cyclohexyl ethyl ketone and 1-cyclohexyl ethyl alcohol and benzyl carbinol generation hydrogenolysis produce.Therefore, the hydrogenation selectivity improving benzyl carbinol becomes the key of hydrogenation of acetophenone reaction.Usual sodium borohydride, the method that benzyl carbinol is prepared in tetrahydro lithium aluminium or aluminium isopropoxide reduction no doubt can obtain the unsaturated alcohol of high yield, but product and reducing agent, the separation difficulty such as solvent, the post processing of product comparatively bothers, and it is many to produce refuse, easy contaminated environment.Therefore key develops the catalyst of function admirable at present.And conventional hydrogenation catalyst has precious metals pt, Pd etc. and non-noble metal Ni, Cu, Mo, Fe etc., wherein noble metal catalyst has good activity and selectivity to fragrant nitro compound hydrogenation, can hydrogenation under normal pressure or low pressure again, but price is high, and catalyst life is not long, and therefore By Non-precious Metal Catalysts hydrogenation receives the concern of domestic and international researcher.
The invention provides a kind of simple H
2the hot method of secondary solvent take ethanol as solvent acetic acid nickel or cobalt acetate for the multistage branched nano nickel of precursor power or nanometer cobalt and catalytic hydrogenation reaction such as the hydrogenation reaction such as hydrogenation of acetophenone and hydrogenation of chloronitrobenzene has good catalytic effect.
Summary of the invention
The object of the invention is to provide a kind of H
2the hot legal system of secondary solvent is for high-purity, even monodispersed multistage branched nano nickel and sea urchin shape nanometer cobalt, second branch shape prepared by the method, polypody shape nano nickel magnetic powder and sea urchin shape nanometer cobalt degree of crystallinity high, pattern is even, coercivity power is high, can be widely used in catalytic reaction.
A method for the multistage apparatus derivatorius of synthetic metals nickel, cobalt, is characterized in that comprising the following steps:
Nickel acetate or cobalt acetate are dissolved in absolute ethyl alcohol the solution A forming solution 0.05mol/L ~ 0.1mol/L by step 1.;
Step 2. by oleyl amine by volume point rate 0.2 ~ 0.4 be distributed to ethanol formed solution B, B solution and solution A are mixed to get mixed solution in the ratio that B/A volume ratio is 0.6 ~ 0.7;
Mixed solution, after above-mentioned mixed solution stirs, moves in dynamic response still, after good seal, passes into H by step 3.
2, by H after displacement
2pressure be transferred to 6 ~ 20bar, close steel cylinder air outlet valve;
Dynamic response still mixing speed is transferred to 400r/min by step 4., and temperature arranges 150 DEG C, reaction 3h;
The product obtained washs with ethanol and cyclohexane by step 5. respectively, carries out Magnetic Isolation and finally dries 60 DEG C time;
Wherein when raw material is nickel acetate, by H in step 3
2pressure is transferred to 6bar, then carries out step 4 and step 5, after obtain second branch shape nano nickel;
When raw material is nickel acetate, by H in step 3
2pressure is transferred to 14bar, then carries out step 4 and step 5, obtains polypody shape nano nickel;
When raw material is cobalt acetate, H in step 3
2pressure is transferred to 10bar; Then carry out step 4 and step 5, obtain sea urchin shape-A nanometer cobalt; H in step 3
2pressure is transferred to 20bar; Then carry out step 4 and step 5, obtain sea urchin shape-B nanometer cobalt.
Multistage branched nano nickel preparation technology: first, 1 ~ 2mmol nickel acetate is dissolved in ethanolic solution, after by oleyl amine by volume point rate 0.2 ~ 0.4 be distributed in ethanolic solution, then two kinds of solution to be poured in dynamic high-pressure reactor, pass into H
2after displacement, and then pass into 3 ~ 20barH
2, close steel cylinder, be placed in 150 DEG C of insulation 3h under agitation, finally, last cool to room temperature, to collect after mother liquor washing and precipitating thing repeatedly, is separated, collect, and drying obtains black nano nickel with magnet.
Multistage branched nanometer cobalt preparation technology:
First, 1 ~ 2mmol cobalt acetate is dissolved in ethanolic solution, after by oleyl amine by volume point rate 0.2 ~ 0.4 be distributed in ethanolic solution, then two kinds of solution to be poured in dynamic high-pressure reactor, pass into H
2after displacement, and then pass into 10 ~ 20barH
2, close steel cylinder, be placed in 150 DEG C of insulation 5 ~ 12h under agitation, finally, last cool to room temperature, to collect after mother liquor washing and precipitating thing repeatedly, is separated, collect, and drying obtains black nano cobalt with magnet.
Catalyst activity evaluation method 1-acetophenone catalytic hydrogenation reaction
Catalyst activity is investigated at 50ml stainless steel interval dynamic response still.By acetophenone, still put into by catalyst, and solvent can make ethanol, isopropyl alcohol, n-butanol etc.H is used after autoclave sealing
2replace ten times, to remove the air in still.Heat after the hydrogen of predetermined pressure, mixing speed is 1000r/min, reaction temperature is 80 DEG C, Hydrogen Vapor Pressure is 15bar, the ratio of acetophenone and ethanol is 1:10, the mass fraction adding catalyst is 0.22% ~ 0.36%, and reacted 3h takes out response sample with gas chromatographic analysis benzyl carbinol wherein, acetophenone and the possible content of other products.
Catalyst activity evaluation method 1-By Catalytic Hydrogenation of Nitrobenzene reacts
Catalyst activity is investigated at 50ml stainless steel interval dynamic response still.By nitrobenzene, still put into by catalyst, and solvent is ethanol, uses H after autoclave sealing
2replace ten times, to remove the air in still.Heat after the hydrogen of predetermined certain pressure, mixing speed is 1000r/min, reaction temperature is 120 DEG C, Hydrogen Vapor Pressure is 10bar, the ratio of nitrobenzene and ethanol is 1:3, the mass fraction adding catalyst is 0.14% ~ 0.2%, and reaction 2h takes out response sample with chromatography of gases analysis nitrobenzene wherein, aniline and the possible content of other products.
Accompanying drawing explanation
Fig. 1 is embodiment 1 product XRD collection of illustrative plates
Fig. 2 is that embodiment 1 product TEM schemes
Fig. 3 is embodiment 2 product XRD collection of illustrative plates
Fig. 4 is that example 2 product TEM schemes
Fig. 5 is embodiment 3 product XRD collection of illustrative plates
Fig. 6 is that embodiment 3 product TEM schemes
Fig. 7 is embodiment 4 product XRD collection of illustrative plates
The TEM that Fig. 8 (a) is multiple sea urchin shape nanometer cobalt-A schemes, and Fig. 8 (b) is the TEM figure of two sea urchin shape nanometer cobalt-A, Fig. 8 (b) is that the TEM of three sea urchin shape nanometer cobalt-A schemes
Fig. 9 is embodiment 5 product XRD collection of illustrative plates
Figure 10 is that embodiment 5 product TEM schemes
Figure 11 is that embodiment 6 product TEM schemes
Figure 12 is example 1, the normal temperature magnetic hysteresis line chart of 2,3 products
Figure 13 is example 1, the result of 2,3 product catalysis hydrogenation of acetophenone reactions
Figure 14 is example 1, the result of 2,3 product catalysis nitrobenzene hydrogenations
Table 1 is the catalytic result of example 1 and example 2 and example 3 catalysis acetophenone catalytic hydrogenation and By Catalytic Hydrogenation of Nitrobenzene
[0033] detailed description of the invention:
Concrete embodiment 1
Take 0.291g nickel acetate NiAc
24H
2o is placed in 100ml beaker, measures 20ml absolute ethyl alcohol pour in beaker with graduated cylinder, stirs ten minutes, forms solution A; Separately get a 50ml beaker, measure 10ml ethanol with graduated cylinder respectively, pipette 4ml oleyl amine with liquid-transfering gun and pour in beaker, mixed solution is shaken up.Mixed solution to be poured in A in nickel acetate mixed solution; After above-mentioned mixed solution stirs, mixed liquor is moved in the dynamic response still of 50ml, after good seal, pass into H
2, by H after replacing ten times
2pressure be transferred to 6bar, close steel cylinder air outlet valve; Dynamic response still mixing speed is transferred to 400r/min, and temperature arranges 150 DEG C, obtains second branch shape nano nickel after reaction 3h; The product obtained is washed three times with ethanol and cyclohexane respectively, carries out Magnetic Isolation and finally dry 60 DEG C time, obtain black powder catalyst A.
Concrete embodiment 2
Take 0.291g nickel acetate NiAc
24H
2o is placed in 100ml beaker, measures 20ml absolute ethyl alcohol pour in beaker with graduated cylinder, stirs ten minutes, forms solution A; Separately get a 50ml beaker, measure 10ml ethanol with graduated cylinder respectively, pipette 4ml oleyl amine with liquid-transfering gun and pour in beaker, mixed solution is shaken up.Mixed solution to be poured in A in nickel acetate mixed solution.After above-mentioned mixed solution stirs, mixed liquor is moved in the dynamic response still of 50ml, after good seal, pass into H
2, by H after replacing ten times
2pressure be transferred to 14bar, close steel cylinder air outlet valve; Dynamic response still mixing speed is transferred to 400r/min, and temperature arranges 150 DEG C, obtains polypody shape nano nickel after reaction 3h; The product obtained is washed three times with ethanol and cyclohexane respectively, carries out Magnetic Isolation and finally dry 60 DEG C time, obtain catalyst B.
Concrete embodiment 3
Take 0.291g nickel acetate NiAc
24H
2o is placed in 100ml beaker, measures 20ml absolute ethyl alcohol pour in beaker with graduated cylinder, stirs ten minutes, forms solution A; Separately get a 50ml beaker, measure 10ml ethanol with graduated cylinder respectively, pipette 4ml oleyl amine with liquid-transfering gun and pour in beaker, mixed solution is shaken up.Mixed solution to be poured in A in nickel acetate mixed solution.After above-mentioned mixed solution stirs, moved into by mixed liquor in the dynamic response still of 50ml, after good seal, dynamic response still mixing speed is transferred to 400r/min, and temperature arranges 150 DEG C, obtains nano nickle granules after reaction 3h; The product obtained is washed three times with ethanol and cyclohexane respectively, carries out Magnetic Isolation and finally dry 60 DEG C time, obtain catalyst C.
Concrete embodiment 4
Take 0.248g cobalt acetate CoAc
24H
2o is placed in 100ml beaker, measures 20ml absolute ethyl alcohol pour in beaker with graduated cylinder, stirs ten minutes, forms solution A; Separately get a 50ml beaker, measure 10ml ethanol with graduated cylinder respectively, pipette 4ml oleyl amine with liquid-transfering gun and pour in beaker, mixed solution is shaken up.Mixed solution to be poured in A in nickel acetate mixed solution.After above-mentioned mixed solution stirs, mixed liquor is moved in the dynamic response still of 50ml, after good seal, pass into H
2, by H after replacing ten times
2pressure be transferred to 10bar, close steel cylinder air outlet valve; Dynamic response still mixing speed is transferred to 400r/min, and temperature arranges 150 DEG C, obtains sea urchin shape nanometer cobalt-A after reaction 12h; The product obtained is washed three times with ethanol and cyclohexane respectively, carries out Magnetic Isolation and finally dry 60 DEG C time.
Concrete embodiment 5
Take 0.248g cobalt acetate CoAc
24H
2o is placed in 100ml beaker, measures 20ml absolute ethyl alcohol pour in beaker with graduated cylinder, stirs ten minutes, forms solution A; Separately get a 50ml beaker, measure 10ml ethanol with graduated cylinder respectively, pipette 4ml oleyl amine with liquid-transfering gun and pour in beaker, mixed solution is shaken up.Mixed solution to be poured in A in nickel acetate mixed solution.After above-mentioned mixed solution stirs, mixed liquor is moved in the dynamic response still of 50ml, after good seal, pass into H
2, by H after replacing ten times
2pressure be transferred to 20bar, close steel cylinder air outlet valve; Dynamic response still mixing speed is transferred to 400r/min, and temperature arranges 150 DEG C, obtains sea urchin shape nanometer cobalt-B after reaction 12h; The product obtained is washed three times with ethanol and cyclohexane respectively, carries out Magnetic Isolation and finally dry 60 DEG C time.
Concrete embodiment 6
Take 0.248g cobalt acetate CoAc
24H
2o is placed in 100ml beaker, measures 20ml absolute ethyl alcohol pour in beaker with graduated cylinder, stirs ten minutes, forms solution A; Separately get a 50ml beaker, measure 10ml ethanol with graduated cylinder respectively, pipette 4ml oleyl amine with liquid-transfering gun and pour in beaker, mixed solution is shaken up.Mixed solution to be poured in A in nickel acetate mixed solution.After above-mentioned mixed solution stirs, mixed liquor is moved in the dynamic response still of 50ml, after good seal, pass into H
2, by H after replacing ten times
2pressure be transferred to 10bar, close steel cylinder air outlet valve; Dynamic response still mixing speed is transferred to 400r/min, and temperature arranges 150 DEG C, obtains sea urchin shape nanometer cobalt-A after reaction 5h; The product obtained is washed three times with ethanol and cyclohexane respectively, carries out Magnetic Isolation and finally dry 60 DEG C time.
Hydrogenation of acetophenone active testing: second branch shape or graininess or polypody shape nano nickel catalyst
Catalyst amount is 0.0080g, acetophenone 1ml, n-hexane 10ml, and reaction temperature 80 DEG C, Hydrogen Vapor Pressure 1.5MPa, stir speed (S.S.) 1000rpm, hydrogenation the results are shown in Fig. 8.
As can be seen from the reaction test table 1 obtained, the catalytic activity of polypody shape nano nickel is greater than the catalytic activity of second branch shape nano nickel, be greater than nano nickle granules, this may be greater than graininess nano nickel due to new pattern nano nickel specific area, and this has good application prospect in catalytic hydrogenation field.
Hydrogenation of chloronitrobenzene active testing: second branch shape nano nickel or graininess or polypody shape nano nickel catalyst
Catalyst amount is 0.0150g, nitrobenzene 2.4ml, n-hexane 7.2ml, and reaction temperature 120 DEG C, Hydrogen Vapor Pressure 1.0MPa, stir speed (S.S.) 1000rpm, hydrogenation the results are shown in table 1.
As can be seen from the reaction test result table 1 obtained, the catalytic activity of polypody shape nano nickel is greater than the catalytic activity of second branch shape nano nickel, be greater than nano nickle granules, this and hydrogenation of acetophenone reaction result have and well coincide, thus this has good application prospect in catalytic hydrogenation field to prove multistage branched nano nickel catalyst that this process for synthetic catalyst synthesizes.
Table 1 example 1, example 2 and example 3 catalysis acetophenone, the change of nitrobenzene hydrogenation conversion ratio
Claims (2)
1. the preparation method of metallic nickel, the multistage apparatus derivatorius of cobalt, is characterized in that comprising the following steps:
Nickel acetate or cobalt acetate are dissolved in absolute ethyl alcohol the solution A forming solution 0.05mol/L ~ 0.1mol/L by step 1.;
Step 2. by oleyl amine by volume point rate 0.2 ~ 0.4 be distributed to ethanol formed solution B, B solution and solution A are mixed to get mixed solution in the ratio that B/A volume ratio is 0.6 ~ 0.7;
Mixed solution, after above-mentioned mixed solution stirs, moves in dynamic response still, after good seal, passes into H by step 3.
2, by H after displacement
2pressure be transferred to 6 ~ 20bar, close steel cylinder air outlet valve;
Dynamic response still mixing speed is transferred to 400r/min by step 4., and temperature arranges 150 DEG C, reaction 3h;
The product obtained washs with ethanol and cyclohexane by step 5. respectively, carries out Magnetic Isolation and finally dries 60 DEG C time;
Wherein when raw material is nickel acetate, by H in step 3
2pressure is transferred to 6bar, then carries out step 4 and step 5, after obtain second branch shape nano nickel;
When raw material is nickel acetate, by H in step 3
2pressure is transferred to 14bar, then carries out step 4 and step 5, obtains polypody shape nano nickel;
When raw material is cobalt acetate, H in step 3
2pressure is transferred to 10bar; Then carry out step 4 and step 5, obtain sea urchin shape-A nanometer cobalt; H in step 3
2pressure is transferred to 20bar; Then carry out step 4 and step 5, obtain sea urchin shape-B nanometer cobalt.
2. the application of the multistage apparatus derivatorius of the metallic nickel prepared by method according to claim 1, cobalt, is characterized in that: the application in acetophenone or By Catalytic Hydrogenation of Nitrobenzene reaction.
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| CN104368342B (en) * | 2014-09-21 | 2016-08-17 | 北京化工大学 | A kind of preparation method of nanometer chain cobalt |
| CN104308186B (en) * | 2014-09-28 | 2016-06-15 | 兰州大学 | A kind of method preparing corner star nickel nano material |
| CN104475107B (en) * | 2014-11-28 | 2017-09-29 | 中国科学院上海高等研究院 | The bimetallic sea urchin type catalyst being hydrogenated with for aromatic rings and its preparation method and application |
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| CN101178961B (en) * | 2006-11-10 | 2011-02-09 | 北京万德高科技发展有限公司 | Water soluble magnetic nanometer crystal with high dissolvability and method of producing the same |
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