CN109718775A - A kind of CuCo2O4The preparation method of nano spinel catalyst - Google Patents
A kind of CuCo2O4The preparation method of nano spinel catalyst Download PDFInfo
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- CN109718775A CN109718775A CN201811546214.3A CN201811546214A CN109718775A CN 109718775 A CN109718775 A CN 109718775A CN 201811546214 A CN201811546214 A CN 201811546214A CN 109718775 A CN109718775 A CN 109718775A
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Abstract
The invention belongs to synthesize highly active catalytic reducing catalyst field, in particular to a kind of unformed silica auxiliary preparation CuCo2O4The preparation method of the brilliant catalyst of nanometer point, the specific steps of which are as follows: (1) using copper source, cobalt source, silicon source, ethyl alcohol and deionized water as raw material, forms mixed solution A；(2) high polymer powder is added into mixed solution A, magnetic agitation a few hours to high polymer are completely dissolved, and form solution B；(3) it extracts solution B and carries out electrostatic spraying, spraying compound precursor roasting a few hours is taken to obtain solid D；(4) it will be put into hot alkaline solution and impregnate in solid D, obtain mixed solution E；(5) mixed solution E is through suction filtration, washing, drying to get target product.Present device is simple, process simplification, low in investment cost, and target product catalytic activity is strong, and porosity is high, and stability is good, and crystallite dimension is small.
Description
Technical field
The invention belongs to synthesize highly active catalytic reducing catalyst field, in particular to a kind of unformed silica auxiliary preparation
CuCo2O4The preparation method of the brilliant catalyst of nanometer point.
Background technique
Para-aminophenol (p-aminophenol) can be applied to ANTU as a kind of very important fine chemistry industry material
The medical drugs such as bright, benoral.Chemical catalysis reduction method is that the viable process road of para-aminophenol is prepared based on p-nitrophenol
Diameter, has important application prospect, and can the key of the technique be prepare a kind of highly active catalytic reducing catalyst.Research shows that
The noble metal catalysts such as Pt, Pd, Ag prepare the catalytic activity in para-aminophenol with superelevation in p-nitrophenol reduction, still
The price of noble metal catalyst is higher, and expensive cost limits the popularization and application of noble metal catalyst.
It studies for a long period of time and shows CuCo2O4Spinel oxide material is living with certain catalysis in p-nitrophenol reduction
Property, however the CuCo of conventional method preparation2O4Spinel catalyst catalytic activity is simultaneously not bery high.It is understood that tradition CuCo2O4Point
The preparation method of spar is that then high-temperature roasting obtains CuCo copper, cobalt precursor mixing2O4Spinelle is formed in this way
CuCo2O4Spinel has biggish particle size, and surface can be lower, and catalytic activity is weaker.In order to reduce CuCo2O4Point
The particle size of spinel, Feng et al. are prepared for CuCo by hydrothermal synthesis method2O4Spinel oxide material, the material
With lesser particle size, higher catalytic activity is presented in persulfate activation.Mei etc. passes through urea auxiliary combustion
Method is prepared for the CuCo of nano-scale2O4Oxide presents higher catalytic activity in lithium ion battery Anodic material.
These above-mentioned methods are all to have used hydrothermal synthesis or other complicated technologies, and the aftertreatment technologies such as separating, washing are complex.
Relative to precious metal catalytic material, transition metal-catalyzed material source is extensive, at low cost, is more suitable for industrial metaplasia
It produces, studies have found that the catalytic activity of most transition-metal catalysts is difficult to be equal to noble metal in p-nitrophenol reduction
Beauty, therefore how to optimize the activity transition metal catalyst for preparing suitable p-nitrophenol reduction as research heat in recent years
Point.
Summary of the invention
Simple it is an object of the invention in place of overcome the deficiencies in the prior art, provide a kind of equipment, process simplification is invested
Low in cost, target product catalytic activity is strong, and porosity is high, and stability is good, the small CuCo of crystallite dimension2O4Nano spinel is urged
The preparation method of agent.
In order to solve the above technical problems, the present invention is implemented as follows:
CuCo2O4The preparation method of nano spinel catalyst can successively be implemented as follows:
(1) using copper source, cobalt source, silicon source, ethyl alcohol and deionized water as raw material, mixed solution A is formed；
(2) high polymer powder is added into mixed solution A, magnetic agitation a few hours to high polymer are completely dissolved, and are formed molten
Liquid B；
(3) it extracts solution B and carries out electrostatic spraying, spraying compound precursor roasting a few hours is taken to obtain solid D；
(4) it will be put into hot alkaline solution and impregnate in solid D, obtain mixed solution E；
(5) mixed solution E is through suction filtration, washing, drying to get target product.
2, CuCo according to claim 12O4The preparation method of nano spinel catalyst, it is characterised in that: it is described
Silicon source is the mixture of one or more of tetraethyl orthosilicate, positive silicic acid propyl ester or butyl silicate.
As a preferred embodiment, high polymer is polyvinylpyrrolidone in step (2) of the present invention.
Further, copper source of the present invention is Gerhardite (II).
Further, cobalt source of the present invention is cabaltous nitrate hexahydrate (II).
Further, the present invention is with molar ratio computing, the molar ratio of Gerhardite (II) and cabaltous nitrate hexahydrate (II)
For 1:2.
Further, the volume ratio of ethyl alcohol and deionized water is 1:1 in step (1) of the present invention.
Further, present invention is characterized in that hot alkaline solution is that ammonium hydroxide, NaOH solution or KOH are molten in the step (4)
One of liquid.
Further, soaking temperature is 40 DEG C~80 DEG C in step (4) of the present invention.
The present invention can be good at being applied to nitrophenol reduction, reduce process simplification, equipment, to reduce investment etc.
Problem.The present invention is based on unformed silica material auxiliary to be prepared for CuCo2O4The nano particle of spinel oxide, and pass through
NaOH hot solution has effectively etched away unformed silicon oxide substrate.Prepared CuCo2O4Spinel oxide has nanoparticle
Size, and high degree of dispersion, the CuCo of relatively traditional roasting technique preparation2O4Spinel oxide has smaller partial size.This hair
It is bright through the etched CuCo of NaOH2O4Unformed monox composite oxides catalyst, in terms of p-nitrophenol is catalyzed reduction
Effect is obvious.With the nanoscale CuCo of unformed silica auxiliary preparation2O4Spinel particles, microscopic appearance and particle ruler
The very little CuCo with conventional method preparation2O4It is significantly different, there is higher porosity and smaller crystallite dimension, have higher
Catalytic activity and stability.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and specific embodiments.Protection scope of the present invention not only office
It is limited to the statement of following content.
Fig. 1 is CuCo under the conditions of different disposal of the present invention2O4The XRD diagram of nano spinel catalyst；
Fig. 2 is the p-nitrophenol concentration of three kinds of catalyst of the invention with the change curve in reaction time；
Fig. 3 a is CuCo of the present invention2O4(NaOH processing) surface topography map before the reaction；
Fig. 3 b is CuCo of the present invention2O4(NaOH processing) surface topography map after the reaction.
Specific embodiment
The present invention will be further described below with reference to examples.Material according to the present invention include be not limited to
Statement in lower embodiment.
CuCo of the invention2O4Nano spinel catalyst is through NaOH treated CuCo2O4Silica combined oxidation
Object, water used in following examples is deionized water；Agents useful for same is all made of analytical reagents in addition to special instruction；
In embodiment, using SU8010 scanning electron microscope to CuCo obtained under different condition2O4The microscopic appearance of spinel oxide carries out
Characterization.XRD characterization uses Rigaku company D8AdvanceX x ray diffractometer x, experiment condition are as follows: Cu K α radiation (λ=
0.15418nm), pipe pressure: 40Kv, Guan Liu: 30mA, using continuous scanning mode, 0.02 ° of step-length, 6 ° of sweep speed (2 θ)/min.
Using ultraviolet-visible spectrophotometer (upper Nereid section, L5s) to CuCo obtained under different condition2O4Nano spinel material
Catalytic performance carries out on-line analysis.
Embodiment 1
Weigh Cu (NO3)2.3H2O 0.4832g、Co(NO3)2.6H2O 1.1641g, tetraethyl orthosilicate 0.462g are dissolved in
The mixed solution A that 4ml deionized water and 4ml ethyl alcohol are constituted；Weigh 1.3g PVP (polyvinylpyrrolidone) powder be dissolved in it is above-mentioned
Mixed solution A, magnetic agitation 12h form solution B until PVP is completely dissolved；It is put into electrostatic spinning machine and carries out electrostatic spraying
Nano particle is obtained, electrostatic spraying DC voltage is 20kV, and spray head and receiver distance are 20cm, allow electrostatic particle to be sprayed at and connect
On the aluminium foil for receiving device.Compound precursor after electrostatic spraying is put into 600 DEG C of roasting 5h in crucible, forms solid D；Configuration
The NaOH solution 50ml of 5mol/L, the solid D (CuCo after roasting is added2O4Unformed monox composite oxides) powder, 60
DEG C impregnate 2h, obtain mixed solution E；Be cleaned multiple times with deionized water up to neutral after mixed solution E is filtered, last 50
DEG C dry 8h obtains final product.
Embodiment 2
Weigh Cu (NO3)2.3H2O 0.4832g、Co(NO3)2.6H2O 1.1641g, positive silicic acid propyl ester 0.412g are dissolved in 4ml
The mixed solution A that deionized water and 4ml ethyl alcohol are constituted；It weighs 1.3g PVP (polyvinylpyrrolidone) powder and is dissolved in above-mentioned mixing
Solution A, magnetic agitation 12h form solution B until PVP is completely dissolved；Solution B is extracted with injection needle, is put into electrostatic spinning
Electrostatic spraying is carried out in machine and obtains nano particle, and electrostatic spraying DC voltage is 20kV, and spray head and receiver distance are 20cm, are allowed
Electrostatic particle is sprayed on the aluminium foil of receiver.Compound precursor after electrostatic spraying is put into 700 DEG C of roasting 5h, shape in crucible
At solid D (CuCo2O4Unformed monox composite oxides)；50ml water is added to the CuCo after roasting2O4Unformed oxygen
In SiClx composite oxide power, 50 DEG C of immersion 2h obtain mixed solution E；It is carried out after mixed solution E is filtered with deionized water
It is cleaned multiple times until neutral, last 50 DEG C dry 8h obtain final product.
Embodiment 3
Weigh Cu (NO3)2.3H2O 0.4832g、Co(NO3)2.6H2O 1.1641g, butyl silicate 0.392g are dissolved in 4ml
The mixed solution A that deionized water and 4ml ethyl alcohol are constituted；It weighs 1.3g PVP (polyvinylpyrrolidone) powder and is dissolved in above-mentioned mixing
Solution A, magnetic agitation 12h form solution B until PVP is completely dissolved；Solution B is extracted with injection needle, is put into electrostatic spinning
Electrostatic spraying is carried out in machine and obtains nano particle, and electrostatic spraying DC voltage is 18kV, and spray head and receiver distance are 20cm, are allowed
Electrostatic particle is sprayed on the aluminium foil of receiver.Compound precursor after electrostatic spraying is put into 800 DEG C of roasting 5h, shape in crucible
At solid D (CuCo2O4Unformed monox composite oxides)；The NaOH solution 50ml of 5mol/L is configured, after roasting is added
CuCo2O4Unformed monox composite oxides powder, 80 DEG C of immersion 2h, obtains mixed solution E；After mixed solution E is filtered
Be cleaned multiple times with deionized water until neutral, last 50 DEG C dry 8h obtain final product.Wherein Fig. 1 (a) is pure
CuCo2O4XRD diagram；Fig. 1 (b) is CuCo2O4The XRD diagram of monox composite oxides；Fig. 1 (c) is that treated by NaOH
CuCo2O4The XRD diagram of silica.
It is catalyzed reduction experiment
P-nitrophenol is catalyzed reduction experiment using sodium borohydride as reducing agent, and specific experiment is as follows: will be configured
Concentration is that the sodium borohydride solution of 0.01g/mL is added in 1.5mmol/L p-nitrophenol material solution (wherein experiment holding
The molar ratio of p-nitrophenol and sodium borohydride is 60:1), color after the mixing of p-nitrophenol and reducing agent (sodium borohydride)
Become deep yellow from pale yellow, the pure 100 μ L of CuCo2O4 nano spinel catalyst of concentration 0.5mg/mL is added, and is put into L5s rapidly
In ultraviolet-visible spectrophotometer, 200~500nm range based on ultraviolet-visible spectrophotometer is scanned, measurement pair
The curve that the absorbance of nitrophenol solution changes over time, every 30s multiple scanning, detection reaction object and product absorbance become
Change.Fig. 2 is CuCo2O4The p-nitrophenol concentration of catalyst with the reaction time change curve.
It is understood that for those of ordinary skill in the art, can do in accordance with the technical idea of the present invention
Various other changes and modifications out, and all these changes and deformation all should belong to the protection model of the claims in the present invention
It encloses.
Claims (9)
1. a kind of CuCo2O4The preparation method of nano spinel catalyst, which is characterized in that successively implement as follows:
(1) using copper source, cobalt source, silicon source, ethyl alcohol and deionized water as raw material, mixed solution A is formed；
(2) high polymer powder is added into mixed solution A, magnetic agitation a few hours to high polymer are completely dissolved, and form solution B；
(3) it extracts solution B and carries out electrostatic spraying, spraying compound precursor roasting a few hours is taken to obtain solid D；
(4) it will be put into hot alkaline solution and impregnate in solid D, obtain mixed solution E；
(5) mixed solution E is through suction filtration, washing, drying to get target product.
2. CuCo according to claim 12O4The preparation method of nano spinel catalyst, it is characterised in that: the silicon
Source is the mixture of one or more of tetraethyl orthosilicate, positive silicic acid propyl ester or butyl silicate.
3. CuCo according to claim 22O4The preparation method of nano spinel catalyst, it is characterised in that: the step
Suddenly high polymer is polyvinylpyrrolidone in (2).
4. CuCo according to claim 32O4The preparation method of nano spinel catalyst, it is characterised in that: the copper
Source is Gerhardite (II).
5. CuCo according to claim 42O4The preparation method of nano spinel catalyst, it is characterised in that: the cobalt
Source is cabaltous nitrate hexahydrate (II).
6. CuCo according to claim 52O4The preparation method of nano spinel catalyst, it is characterised in that: with mole
Than meter, the molar ratio of Gerhardite (II) and cabaltous nitrate hexahydrate (II) are 1:2.
7. CuCo according to claim 62O4The preparation method of nano spinel catalyst, it is characterised in that: the step
Suddenly the volume ratio of ethyl alcohol and deionized water is 1:1 in (1).
8. any CuCo according to claim 1~72O4The preparation method of nano spinel catalyst, it is characterised in that:
Hot alkaline solution is one of ammonium hydroxide, NaOH solution or KOH solution in the step (4).
9. CuCo according to claim 82O4The preparation method of nano spinel catalyst, it is characterised in that: the step
Suddenly soaking temperature is 40 in (4)oC~80oC。
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Cited By (7)
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| CN110407639A (en) * | 2019-09-11 | 2019-11-05 | 深圳天玑芯科技有限公司 | A kind of nanoparticle water and the preparation method and application thereof |
| CN111364126A (en) * | 2020-04-27 | 2020-07-03 | 河北镭传科技有限责任公司 | Copper oxide/cobaltosic oxide composite material and preparation method and application thereof |
| CN111389409A (en) * | 2020-04-16 | 2020-07-10 | 浙江大学 | Preparation method and application of bismuth vanadate photocatalyst with surface modified by cobalt-copper oxide |
| CN112275288A (en) * | 2020-09-21 | 2021-01-29 | 郑州大学 | Preparation method and application of copper-cobalt oxide-loaded carbon nanofiber composite material |
| CN114250357A (en) * | 2020-09-22 | 2022-03-29 | 中冶长天国际工程有限责任公司 | High-hydrogen low-carbon sinter bed structure, sintering system and method |
| CN114574807A (en) * | 2022-02-28 | 2022-06-03 | 广东鼎泰高科技术股份有限公司 | Plasma transmission device |
| CN115254116A (en) * | 2022-08-12 | 2022-11-01 | 浙江工业大学 | Modified cobalt-based metal oxide/halloysite composite material and application thereof |
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Cited By (11)
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| CN110407639A (en) * | 2019-09-11 | 2019-11-05 | 深圳天玑芯科技有限公司 | A kind of nanoparticle water and the preparation method and application thereof |
| CN111389409A (en) * | 2020-04-16 | 2020-07-10 | 浙江大学 | Preparation method and application of bismuth vanadate photocatalyst with surface modified by cobalt-copper oxide |
| CN111389409B (en) * | 2020-04-16 | 2021-03-30 | 浙江大学 | Preparation method and application of bismuth vanadate photocatalyst with surface modified by cobalt-copper oxide |
| CN111364126A (en) * | 2020-04-27 | 2020-07-03 | 河北镭传科技有限责任公司 | Copper oxide/cobaltosic oxide composite material and preparation method and application thereof |
| CN112275288A (en) * | 2020-09-21 | 2021-01-29 | 郑州大学 | Preparation method and application of copper-cobalt oxide-loaded carbon nanofiber composite material |
| CN112275288B (en) * | 2020-09-21 | 2023-04-14 | 郑州大学 | Preparation method and application of copper-cobalt oxide loaded carbon nanofiber composite material |
| CN114250357A (en) * | 2020-09-22 | 2022-03-29 | 中冶长天国际工程有限责任公司 | High-hydrogen low-carbon sinter bed structure, sintering system and method |
| CN114250357B (en) * | 2020-09-22 | 2023-07-25 | 中冶长天国际工程有限责任公司 | High-hydrogen low-carbon sintering material layer structure, sintering system and method |
| CN114574807A (en) * | 2022-02-28 | 2022-06-03 | 广东鼎泰高科技术股份有限公司 | Plasma transmission device |
| CN115254116A (en) * | 2022-08-12 | 2022-11-01 | 浙江工业大学 | Modified cobalt-based metal oxide/halloysite composite material and application thereof |
| CN115254116B (en) * | 2022-08-12 | 2023-09-05 | 浙江工业大学 | Modified cobalt-based metal oxide/halloysite composite material and application thereof |
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