CN109821548B - Preparation method of composite metal catalyst - Google Patents
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Abstract
The invention discloses a preparation method of a composite metal catalyst, which comprises the following steps: adding copper chloride, bismuth trioxide and distilled water into a reactor, and stirring to obtain a premixed solution; adding oleylamine, normal hexane and phenol into the premixed liquid, heating to 40-50 ℃ under the stirring action, carrying out heat preservation reaction for 2-3 h, and cooling to room temperature to obtain reaction liquid with solid matters; separating solid matters in the reaction liquid, and washing to obtain a solid mixture; and mixing and grinding the solid mixture and sodium sulfate, calcining at the temperature of 350-400 ℃ for 2-3 h, cooling, and washing and drying a calcined product to obtain the composite metal catalyst. The nano-copper and the bismuth trioxide are compounded through a chemical reaction, and the obtained composite material can be used as a photocatalyst with excellent photocatalytic performance.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to the technical field of metal catalyst preparation, and specifically relates to a preparation method of a composite metal catalyst.
Background
The nano copper-based material is a very important transition metal oxide nano material, and has potential application value in various aspects such as gas sensors, catalysis, lithium ion batteries, heavy metal adsorption and the like. Compared with other transition metal oxide nano materials, the nano copper-based material has low price, is environment-friendly and has high catalytic activity, so that the nano copper-based material becomes a hot point of research of people. In recent years, copper-based nano-materials with different shapes and sizes have been synthesized by adopting different synthesis methods, and the application of the copper-based nano-materials in various fields is researched. The previous researches show that the properties of the material in various aspects can be improved by developing different synthesis methods and effectively controlling the appearance, the size, the composition, the specific surface area and the like of the nano material, but the photocatalytic property of the nano copper-based material prepared by the existing synthesis method is still to be further improved when the nano copper-based material is used as a photocatalyst.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a composite metal catalyst, aiming at improving the photocatalytic performance of a photocatalyst.
In order to achieve the above object, the present invention provides a method for preparing a composite metal catalyst, comprising the steps of:
adding copper chloride, bismuth trioxide and distilled water into a reactor, and stirring to obtain a premixed solution;
adding oleylamine, normal hexane and phenol into the premixed liquid, heating to 40-50 ℃ under the stirring action, carrying out heat preservation reaction for 2-3 h, and cooling to room temperature to obtain reaction liquid with solid matters;
separating solid matters in the reaction liquid, and washing to obtain a solid mixture;
and mixing and grinding the solid mixture and sodium sulfate, calcining at the temperature of 350-400 ℃ for 2-3 h, cooling, and washing and drying a calcined product to obtain the composite metal catalyst.
Optionally, the mass ratio of the copper chloride to the bismuth trioxide to the oleylamine to the n-hexane to the phenol is (10-200): (5-50): (5-15): (3-6): (3-9).
Optionally, the step of separating solid substances in the reaction solution and then washing to obtain a solid mixture comprises:
and centrifuging the reaction solution, and washing the separated solid matters to obtain a solid mixture.
Optionally, after centrifuging the reaction solution, washing the separated solid substance to obtain a solid mixture, wherein:
the centrifugal rotating speed during centrifugation is 2000-5000 r/min, and the centrifugation time is 10-15 min.
Optionally, after centrifuging the reaction solution, washing the separated solid substance to obtain a solid mixture, wherein:
the separated solid matter is washed by using distilled water for 5 to 8 times.
Optionally, the solid mixture is mixed with sodium sulfate and ground, then calcined at 350-400 ℃ for 2-3 h, cooled, and then washed and dried to obtain the composite metal catalyst, wherein the step of obtaining the composite metal catalyst comprises:
the mass ratio of the solid mixture to the sodium sulfate is 1: (0.6-1.1).
Optionally, the solid mixture is mixed with sodium sulfate and ground, then calcined at 350-400 ℃ for 2-3 h, cooled, and then washed and dried to obtain the composite metal catalyst, wherein the step of obtaining the composite metal catalyst comprises:
and washing the calcined product for 2-4 times by using a mixed solution of distilled water and ethanol, wherein the mass ratio of the distilled water to the ethanol in the mixed solution is (2-4): 1.
optionally, the solid mixture is mixed with sodium sulfate and ground, then calcined at 350-400 ℃ for 2-3 h, cooled, and then washed and dried to obtain the composite metal catalyst, wherein the step of obtaining the composite metal catalyst comprises:
and drying the calcined product at the drying temperature of 80-90 ℃ for 30-40 min.
According to the technical scheme provided by the invention, copper chloride, bismuth trioxide, oleylamine, n-hexane and phenol are selected as reaction raw materials, and a series of chemical reactions are carried out to obtain the composite material of nano copper and bismuth trioxide, wherein the nano copper and the bismuth trioxide are good photocatalysts, and after the composite material is formed through the reactions, the composite material can utilize the difference of valence band and conduction band energy levels of the two photocatalysts, after the surface receives light radiation, the two substances can simultaneously jump, and partial electron jump between the two substances can effectively reduce the recombination rate of electron-hole, so that the photochemical activity is improved, and the effect of improving the photocatalytic performance is achieved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart of an embodiment of a method for preparing a composite metal catalyst according to the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The nano copper-based material is a very important transition metal oxide nano material, and has potential application value in various aspects such as gas sensors, catalysis, lithium ion batteries, heavy metal adsorption and the like. Researches show that the nano copper-based material with different shapes and sizes can be synthesized by doping different metals or metal oxides, the shapes, sizes, compositions, specific surface areas and the like of the nano copper-based material can be effectively controlled to improve the performances of the nano copper-based material in various aspects, but the photocatalytic performance of the nano copper-based material still needs to be further improved.
In view of this, the present invention provides a method for preparing a composite metal catalyst, in which nano-copper and bismuth trioxide are chemically reacted to form a composite material, so as to achieve the effect of improving the photocatalytic performance, and fig. 1 shows an embodiment of the method for preparing a composite metal catalyst provided by the present invention. Referring to fig. 1, in this embodiment, the preparation method of the composite metal catalyst includes the following steps:
step S10, adding copper chloride, bismuth trioxide and distilled water into a reactor, and stirring to obtain a premixed solution;
step S20, adding oleylamine, n-hexane and phenol into the premixed liquid, heating to 40-50 ℃ under the stirring action, carrying out heat preservation reaction for 2-3 h, and cooling to room temperature to obtain reaction liquid with solid matters;
in specific implementation, the copper chloride and the bismuth trioxide are added into the reactor, and then the distilled water is added for stirring, wherein the stirring manner and the stirring condition are not particularly limited, for example, the stirring manner and the stirring condition may be mechanical stirring or ultrasonic stirring, as long as the copper chloride and the bismuth trioxide are fully dispersed in the distilled water to obtain the premixed liquid, in this embodiment, the mechanical stirring may be performed at a rotation speed of 200 to 500r/min for 20 to 30min to obtain the premixed liquid; and adding oleylamine, normal hexane and phenol into the premixed liquid, heating while stirring, wherein the stirring mode is preferably ultrasonic stirring, for example, the reactor can be placed in an ultrasonic stirrer with the temperature set to be 40-50 ℃, the temperature is kept for reaction for 2-3 hours after the temperature is raised to 40-50 ℃, and the reaction liquid is obtained after the reaction is naturally cooled to room temperature. Wherein the n-hexane is used as a solvent; the oleylamine is used as a reducing agent and also has a certain dispersing effect on the bismuth trioxide; the phenol is a ligand, forms a complex with copper ions and is easily reduced into a nano copper-based material by oleylamine; the addition of the three reagents enables the particles of the produced nano copper-based composite material to be finer and the particle sizes to be more uniform, thereby obtaining a solid product of the nano copper-based composite catalyst. Further, the addition ratio of the raw materials is as follows: the mass ratio of the copper chloride to the bismuth trioxide to the oleylamine to the n-hexane to the phenol is (10-200): (5-50): (5-15): (3-6): (3-9), wherein the n-hexane is in a liquid state, and the mass can be converted into volume according to the density (the density at normal temperature and normal pressure is 0.66g/mL) during addition, so that the measurement is more convenient.
Step S30, separating solid substances in the reaction liquid and then washing to obtain a solid mixture;
in this embodiment, solid substances generated in the reaction are preferably separated by centrifugation, which has the advantages of high solid-liquid separation efficiency and simple operation, and in the specific operation, the reaction solution is preferably centrifuged by selecting parameters of 2000 to 5000r/min of centrifugation speed and 10 to 15min of centrifugation time, so as to obtain a solid product generated in step S20. Further, after the reaction solution is centrifuged, the separated solid matter is washed by distilled water, preferably 5-8 times, and a solid mixture is obtained after washing.
And step S40, mixing and grinding the solid mixture and sodium sulfate, calcining at the temperature of 350-400 ℃ for 2-3 h, cooling, and washing and drying the calcined product to obtain the composite metal catalyst.
The sodium sulfate serves as a calcination auxiliary agent in the calcination process, so that the nano-copper and the bismuth trioxide are combined into a more stable composite material, and in specific implementation, the solid mixture and the sodium sulfate are mixed according to the weight ratio of 1: (0.6-1.1), grinding the mixture in a grinder for 20-30 min to obtain a mixed solid, then putting the mixed solid in a muffle furnace to calcine the mixed solid, naturally cooling the calcined solid to room temperature after the calcination is finished, and washing a calcined product by using a mixed solution of distilled water and ethanol, wherein the mass ratio of the distilled water to the ethanol in the mixed solution is (2-4): 1, preferably 3:1, repeatedly washing for 2-4 times, and drying the washed product at the temperature of 80-90 ℃ for 30-40 min to obtain the composite metal catalyst.
According to the technical scheme provided by the invention, copper chloride, bismuth trioxide, oleylamine, n-hexane and phenol are selected as reaction raw materials, and a composite material consisting of nano copper and bismuth trioxide is obtained after a series of chemical reactions, wherein the nano copper and the bismuth trioxide are good photocatalysts, and after the composite material is formed through the reactions, the composite material can utilize the difference between the valence band and conduction band energy levels of the two photocatalysts, after the surface receives light radiation, the two substances can simultaneously jump, and partial electron jump between the two substances can effectively reduce the recombination rate of electron-hole, so that the photochemical activity is improved, and the effect of improving the photocatalytic performance is achieved; when the preparation method of the composite metal catalyst is applied to industrial production, part of organic pollutants in raw materials used in the preparation process can be degraded quickly, and the reduction of environmental pollution is facilitated.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Adding 10g of copper chloride and 5g of bismuth trioxide into a reactor, adding distilled water, and stirring for 20 min;
(2) sequentially adding 5g of oleylamine, 5mL of n-hexane and 3g of phenol into a reactor, ultrasonically stirring while raising the temperature to 40 ℃, keeping the temperature unchanged, stirring for reacting for 2 hours, and naturally cooling to room temperature;
(3) centrifuging reaction liquid in a reactor for 15min at the rotating speed of 5000r/min, repeatedly washing for 5 times by using distilled water to obtain a solid mixture, mixing and grinding the solid mixture and sodium sulfate according to the mass ratio of 1:0.6 for 30min, placing the mixture in a muffle furnace at 350 ℃ for calcining for 3h, naturally cooling after calcining, washing a calcined product for 2 times by using a mixed solution formed by mixing distilled water and ethanol according to the mass ratio of 3:1, and drying for 30min at the temperature of 90 ℃ after washing to obtain the composite metal catalyst.
Example 2
(1) Adding 200g of copper chloride and 50g of bismuth trioxide into a reactor, adding distilled water, and stirring for 30 min;
(2) sequentially adding 15g of oleylamine, 9mL of n-hexane and 9g of phenol into a reactor, ultrasonically stirring while raising the temperature to 50 ℃, keeping the temperature unchanged, stirring for reacting for 3 hours, and naturally cooling to room temperature;
(3) centrifuging reaction liquid in a reactor for 10min at the rotating speed of 2000r/min, repeatedly washing with distilled water for 8 times to obtain a solid mixture, mixing and grinding the solid mixture and sodium sulfate according to the mass ratio of 1:1.1 for 20min, placing in a 400 ℃ muffle furnace for calcining for 2h, naturally cooling after calcining, washing a calcined product for 4 times by using a mixed solution formed by mixing distilled water and ethanol according to the mass ratio of 3:1, and drying at the temperature of 80 ℃ for 340min after washing to obtain the composite metal catalyst.
Example 3
(1) Adding 110g of copper chloride and 25g of bismuth trioxide into a reactor, adding distilled water, and stirring for 25 min;
(2) sequentially adding 10g of oleylamine, 8mL of n-hexane and 7g of phenol into a reactor, ultrasonically stirring while raising the temperature to 45 ℃, keeping the temperature unchanged, stirring for reacting for 2.5 hours, and naturally cooling to room temperature; (3) centrifuging reaction liquid in a reactor for 14min at the rotating speed of 3000r/min, repeatedly washing for 7 times by using distilled water to obtain a solid mixture, mixing and grinding the solid mixture and sodium sulfate according to the mass ratio of 1:0.8 for 26min, placing the mixture in a muffle furnace at 360 ℃ for calcining for 3h, naturally cooling after calcining, washing a calcined product for 3 times by using a mixed solution formed by mixing distilled water and ethanol according to the mass ratio of 3:1, and drying for 36min at the temperature of 85 ℃ after washing to obtain the composite metal catalyst.
Example 4
(1) Adding 150g of copper chloride and 40g of bismuth trioxide into a reactor, adding distilled water, and stirring for 26 min;
(2) sequentially adding 11g of oleylamine, 7mL of n-hexane and 5g of phenol into a reactor, ultrasonically stirring while raising the temperature to 44 ℃, keeping the temperature unchanged, stirring for reacting for 2.3 hours, and naturally cooling to room temperature;
(3) centrifuging reaction liquid in a reactor for 13min at the rotating speed of 4000r/min, repeatedly washing for 7 times by using distilled water to obtain a solid mixture, mixing and grinding the solid mixture and sodium sulfate according to the mass ratio of 1:1.0 for 24min, placing the mixture in a muffle furnace at 370 ℃ for calcination for 2h, naturally cooling after calcination, washing a calcined product for 3 times by using a mixed solution formed by mixing distilled water and ethanol according to the mass ratio of 2:1, and drying for 38min at the temperature of 86 ℃ after washing to obtain the composite metal catalyst.
Example 5
(1) Adding 180g of copper chloride and 30g of bismuth trioxide into a reactor, adding distilled water, and stirring for 28 min;
(2) sequentially adding 12g of oleylamine, 6mL of n-hexane and 4g of phenol into a reactor, ultrasonically stirring while raising the temperature to 46 ℃, keeping the temperature unchanged, stirring for reacting for 2.2 hours, and naturally cooling to room temperature;
(3) centrifuging reaction liquid in a reactor for 12min at the rotating speed of 3000r/min, repeatedly washing for 6 times by using distilled water to obtain a solid mixture, mixing and grinding the solid mixture and sodium sulfate according to the mass ratio of 1:0.9 for 23min, placing the mixture in a muffle furnace at 380 ℃ for calcination for 2.5h, naturally cooling after calcination, washing a calcined product for 3 times by using a mixed solution formed by mixing distilled water and ethanol according to the mass ratio of 4:1, and drying for 34min at 82 ℃ after washing to obtain the composite metal catalyst.
In order to further illustrate the beneficial effects of the present invention, the composite metal catalyst and the nano copper material prepared in examples 1 to 5 of the present invention were subjected to a photocatalytic experiment with the nano copper material as a comparative example, and the photocatalytic performance was verified by the following specific method:
accurately weighing 0.0500g of methylene blue, preparing a methylene blue solution with the concentration of 10.00mg/L by using a 500mL volumetric flask, taking five parts of 50mL of methyl blue solution, then respectively taking nano copper materials and 50mg of the composite metal catalyst materials prepared in the examples 1 to 5 into seven large quartz tubes, correspondingly putting the seven large quartz tubes into the seven large quartz tubes, and pasting a label on each large quartz tube (taking one part of the methylene blue solution as a blank control without putting any photocatalyst). Dark reaction is carried out in a photochemical reactor for 0.5h to ensure that the system reaches a saturated state, about 5mL of reaction liquid is absorbed by a suction pipe, and after a solid catalyst is separated by a centrifugal machine, the absorbance of the supernatant solution is measured as A0; then, the 500W mercury lamp was turned on, about 5mL of the reaction solution was sucked up with a pipette every half hour, the solid catalyst was separated with a centrifuge, the supernatant solution was taken with reference to a blank liquid, and the absorbance At 664nm was measured with a spectrophotometer and recorded for 3 hours in total. The degradation rate of each catalyst was calculated according to the calculation formula W (%) - (a 0-At)/a 0 × 100%, and the calculation results are shown in table 1 below.
TABLE 1 degradation rate calculation results for catalysts
As can be seen from the results in table 1, compared with the method that the nano copper material is directly used as the photocatalyst, the degradation rate of the composite metal catalyst is higher, which indicates that the composite metal catalyst prepared in the embodiment of the present invention has higher photochemical activity and better photocatalytic performance.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (7)
1. The preparation method of the composite metal catalyst is characterized by comprising the following steps of:
adding copper chloride, bismuth trioxide and distilled water into a reactor, and stirring to obtain a premixed solution;
adding oleylamine, normal hexane and phenol into the premixed liquid, heating to 40-50 ℃ under the stirring action, then carrying out heat preservation reaction for 2-3 h, and cooling to room temperature to obtain a reaction liquid with solid matters, wherein the mass ratio of the cupric chloride, the bismuth trioxide, the oleylamine, the normal hexane and the phenol is (10-200): (5-50): (5-15): (3-6): (3-9);
separating solid matters in the reaction liquid, and washing to obtain a solid mixture;
and mixing and grinding the solid mixture and sodium sulfate, calcining at the temperature of 350-400 ℃ for 2-3 h, cooling, and washing and drying a calcined product to obtain the composite metal catalyst.
2. The method of preparing the composite metal catalyst according to claim 1, wherein the step of separating solid materials from the reaction solution and washing the separated solid materials to obtain a solid mixture comprises:
and centrifuging the reaction solution, and washing the separated solid matters to obtain a solid mixture.
3. The method for preparing a composite metal catalyst according to claim 2, wherein the step of centrifuging the reaction solution and washing the separated solid substance to obtain a solid mixture comprises:
the centrifugal rotating speed during centrifugation is 2000-5000 r/min, and the centrifugation time is 10-15 min.
4. The method for preparing a composite metal catalyst according to claim 2, wherein the step of centrifuging the reaction solution and washing the separated solid substance to obtain a solid mixture comprises:
the separated solid matter is washed by using distilled water for 5 to 8 times.
5. The method for preparing the composite metal catalyst according to claim 1, wherein the solid mixture is mixed with sodium sulfate and ground, then calcined at 350-400 ℃ for 2-3 h, then cooled, and then the calcined product is washed and dried to obtain the composite metal catalyst, and the method comprises the steps of:
the mass ratio of the solid mixture to the sodium sulfate is 1: (0.6-1.1).
6. The method for preparing the composite metal catalyst according to claim 1, wherein the solid mixture is mixed with sodium sulfate and ground, then calcined at 350-400 ℃ for 2-3 h, then cooled, and then the calcined product is washed and dried to obtain the composite metal catalyst, and the method comprises the steps of:
and washing the calcined product for 2-4 times by using a mixed solution of distilled water and ethanol, wherein the mass ratio of the distilled water to the ethanol in the mixed solution is (2-4): 1.
7. the method for preparing the composite metal catalyst according to claim 1, wherein the solid mixture is mixed with sodium sulfate and ground, then calcined at 350-400 ℃ for 2-3 h, then cooled, and then the calcined product is washed and dried to obtain the composite metal catalyst, and the method comprises the steps of:
and drying the calcined product at the drying temperature of 80-90 ℃ for 30-40 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974365A (en) * | 2012-12-12 | 2013-03-20 | 天津工业大学 | Method for preparing load type high-dispersion multi-component precious metal nanoparticle catalyst |
| CN104607200A (en) * | 2015-01-05 | 2015-05-13 | 延安大学 | Copper/bismuth tungstate composite photocatalytic material and preparation method thereof |
| CN104801294A (en) * | 2015-05-14 | 2015-07-29 | 北京石油化工学院 | Preparation method of bismuth trioxide nanosphere |
| CN107626298A (en) * | 2017-09-29 | 2018-01-26 | 盐城工学院 | A kind of bismuth based semiconductor photochemical catalyst and preparation method thereof |
| CN108722428A (en) * | 2018-06-04 | 2018-11-02 | 朱修齐 | A kind of composite material and its application for photocatalytic degradation organic matter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974365A (en) * | 2012-12-12 | 2013-03-20 | 天津工业大学 | Method for preparing load type high-dispersion multi-component precious metal nanoparticle catalyst |
| CN104607200A (en) * | 2015-01-05 | 2015-05-13 | 延安大学 | Copper/bismuth tungstate composite photocatalytic material and preparation method thereof |
| CN104801294A (en) * | 2015-05-14 | 2015-07-29 | 北京石油化工学院 | Preparation method of bismuth trioxide nanosphere |
| CN107626298A (en) * | 2017-09-29 | 2018-01-26 | 盐城工学院 | A kind of bismuth based semiconductor photochemical catalyst and preparation method thereof |
| CN108722428A (en) * | 2018-06-04 | 2018-11-02 | 朱修齐 | A kind of composite material and its application for photocatalytic degradation organic matter |
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