CN114832827B - Preparation method of directional heteroepitaxy composite catalyst by utilizing magnetocaloric effect - Google Patents
Preparation method of directional heteroepitaxy composite catalyst by utilizing magnetocaloric effect Download PDFInfo
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- CN114832827B CN114832827B CN202210539319.6A CN202210539319A CN114832827B CN 114832827 B CN114832827 B CN 114832827B CN 202210539319 A CN202210539319 A CN 202210539319A CN 114832827 B CN114832827 B CN 114832827B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000001534 heteroepitaxy Methods 0.000 title claims abstract description 35
- 230000000694 effects Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 39
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 18
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 13
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000006260 foam Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000006249 magnetic particle Substances 0.000 claims description 4
- 230000001351 cycling effect Effects 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/33—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Abstract
The invention discloses a preparation method of a directional heteroepitaxy composite catalyst by utilizing a magnetocaloric effect. Belongs to the technical field of catalysts, and comprises the following steps: preparing a precursor solution by zinc acetate dihydrate, potassium hydroxide and sodium citrate dihydrate; placing a magnetic substrate in a precursor solution, performing magnetocaloric reaction under the action of an alternating magnetic field, and enabling crystals to grow on the surface of the magnetic substrate in an oriented manner through local high temperature generated on the surface of the magnetic substrate to generate a composite catalyst; taking out the composite catalyst for annealing; after the catalyst is subjected to a plurality of cyclic processes of magnetocaloric crystallization and re-annealing, zinc oxide crystals can be effectively grown on magnetic substrates such as iron/cobalt/nickel base and the like in a directional heteroepitaxy mode. The invention can obtain the heteroepitaxial composite catalyst with good crystallinity, regular arrangement and directional growth. The method is easy to operate, has good repeatability, solves the problem of heteroepitaxial crystal growth on the magnetic substrate, and has certain industrial application prospect in the fields of photocatalysis, electrocatalysis, thermocatalysis and the like.
Description
Technical Field
The invention belongs to the technical field of catalysts, relates to a preparation method of a directional heteroepitaxy composite catalyst by utilizing a magnetocaloric effect, and in particular relates to a preparation method for enabling zinc oxide crystals to grow on a certain magnetic substrate (iron/cobalt/nickel-based foam metal, a magnetic metal plate, large-size magnetic particles and the like) in a directional heteroepitaxy mode by utilizing magnetocaloric effect cyclic crystallization.
Background
In recent years, zinc oxide (ZnO) has become an excellent photocatalyst among metal oxides due to its excellent semiconductor optical properties, non-toxicity, economical efficiency, ease of synthesis, and the like. In addition, although the nano zinc oxide of the microparticles plays an important role in the catalytic field, the nano zinc oxide releases free radicals, thereby increasing oxidation pressure and damaging proteins, esters and DNA in the body. Thus, such defects can be effectively avoided by fixedly growing zinc oxide on a certain substrate.
Along with the continuous abundance of technical means, various zinc oxide-based composite catalyst preparation methods are mature day by day, however, the traditional methods such as a hydrothermal method, a precipitation method and an impregnation method are difficult to effectively grow zinc oxide on another substrate in a directional heteroepitaxy manner, and the defects of easy falling, low composite efficiency, difficult recycling and the like exist.
According to the magnetocaloric effect of magnetic material in alternating magnetic field, local high temperature can be produced on the surface of the magnetic material to accelerate the crystallization process of crystal, so that the crystal can be grown on the surface of magnetic substrate in a directional manner.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a directional heteroepitaxy composite catalyst by utilizing a magnetocaloric effect, which is characterized in that crystals such as zinc oxide grow on the surface of a magnetic substrate in a directional heteroepitaxy manner by utilizing the magnetocaloric effect generated by the magnetic substrate in an alternating magnetic field and circulating crystallization through the magnetocaloric effect, so that the directional heteroepitaxy composite catalyst is synthesized. By using the method, the heteroepitaxial composite catalyst with good crystallinity, regular arrangement and directional growth can be obtained. The method is simple, easy to operate, good in repeatability and capable of large-scale production, solves the problem of heteroepitaxial crystal growth on the magnetic substrate, and has a certain industrial application prospect in the fields of photocatalysis, electrocatalysis, thermocatalysis and the like.
The technical scheme of the invention is as follows: according to the preparation method of the directional heteroepitaxy composite catalyst by utilizing the magnetocaloric effect, the magnetocaloric effect generated by the magnetic substrate in an alternating magnetic field is utilized, and then the crystal is grown on the surface of the magnetic substrate by the directional heteroepitaxy through the cyclic crystallization of the magnetocaloric effect, so that the directional heteroepitaxy composite catalyst is synthesized;
the preparation method comprises the following specific steps:
step (1), preparing precursor solution by adding prepared zinc acetate dihydrate, potassium hydroxide and sodium citrate dihydrate into water,
step (2), preparing a magnetic substrate, preprocessing, placing the magnetic substrate in a precursor solution, performing magnetocaloric reaction under the action of an alternating magnetic field, and enabling crystals to grow directionally on the surface of the magnetic substrate through local high temperature generated on the surface of the magnetic substrate, so as to generate a composite catalyst;
step (3), taking out the composite catalyst from the precursor solution and annealing;
and (4) cycling the steps for a plurality of times, and enabling the zinc oxide crystal to grow on the magnetic substrate in a directional heteroepitaxy manner after the composite catalyst repeatedly undergoes a magnetocaloric crystallization and re-annealing process.
Further, in the step (1), the molar ratio of zinc acetate dihydrate to potassium hydroxide is 5: 1-2: 1, a step of; the molar ratio of zinc acetate dihydrate to sodium citrate dihydrate is 1:1 to 1:2; the water is deionized water.
Further, in the step (1), the reaction temperature of the prepared precursor solution is 65-85 ℃ and the reaction time is 2-8 h.
Further, in the step (2), the magnetic substrate is one of iron/cobalt/nickel-based-foam metal, a magnetic metal plate and large-sized magnetic particles.
Further, in the step (2), the frequency of the alternating magnetic field is 10 -1 ～10 5 Hz, the magnetic field intensity is 0.1-100 mT.
Further, in the step (2), the time of the magnetocaloric reaction is 0.5 to 8 hours, and the reaction temperature is 80 to 240 ℃.
Further, in the step (3), the annealing temperature is 180-220 ℃ and the annealing time is 1-4 h.
Further, in the step (4), the number of the circulation steps is 2 to 5.
The beneficial effects of the invention are as follows: the invention is characterized in that: the method is simple, easy to operate, good in repeatability and capable of large-scale production, solves the problem of heteroepitaxial growth of crystals on the magnetic substrate, and effectively solves the defects of damage to proteins, esters, DNA and the like in a body due to the fact that nano zinc oxide is released into the environment to increase oxidation pressure by directional heteroepitaxial growth on the magnetic substrate; in addition, compared with the traditional methods such as a hydrothermal method, a precipitation method, a dipping method and the like, zinc oxide is difficult to grow on another substrate in a directional heteroepitaxy manner, and the defects of easy falling, low composite efficiency, difficult recycling and the like exist.
Drawings
FIG. 1 is a flow chart of the operation of the present invention;
FIG. 2 is a scanning electron microscope image of a foam nickel@zinc oxide oriented heteroepitaxial composite catalyst prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a nickel plate @ zinc oxide oriented heteroepitaxial composite catalyst prepared in example 2 of the present invention.
Detailed Description
In order to more clearly describe the technical scheme of the invention, the technical scheme of the invention is further described in detail below with reference to the accompanying drawings:
as shown in the figure, the invention utilizes the magnetocaloric effect generated by the magnetic substrate in the alternating magnetic field, and enables crystals such as zinc oxide and the like to grow on the surface of the magnetic substrate in a directional heteroepitaxy manner through cyclic crystallization of the magnetocaloric effect, so as to synthesize the directional heteroepitaxy composite catalyst; the specific operation steps are as follows:
1. zinc acetate dihydrate, potassium hydroxide and sodium citrate dihydrate are used as precursors, and added into deionized water to prepare a precursor solution;
2. placing a magnetic substrate (foam nickel) in a precursor solution, performing magnetocaloric reaction under the action of an alternating magnetic field, and enabling crystals to grow directionally on the surface of the magnetic substrate through local high temperature generated on the surface of the magnetic substrate to generate a composite catalyst;
3. taking out the composite catalyst from the precursor solution and annealing;
4. and (3) cycling the steps for a plurality of times, and repeatedly carrying out magnetocaloric crystallization and re-annealing on the catalyst to enable zinc oxide crystals to grow on the magnetic substrate in a directional heteroepitaxy mode.
The alternating magnetic field used in the invention has the frequency of 10 -1 ～10 5 Hz, the magnetic field intensity is 0.1-100 mT.
The magnetic substrate used in the invention is iron/cobalt/nickel-based foam metal, a magnetic metal plate, large-size magnetic particles and the like.
The reaction temperature of the precursor solution used in the invention is 65-85 ℃ and the reaction time is 2-8 h.
The molar ratio of zinc acetate dihydrate to sodium citrate dihydrate used in the invention is 1:1 to 1:2, zinc acetate dihydrate and potassium hydroxide in a molar ratio of 1:1 to 1:2.
the magnetocaloric reaction time used in the invention is 0.5-8 h, and the reaction temperature is 80-240 ℃.
The annealing temperature used in the invention is 180-220 ℃, and the annealing time is 1-4 h.
The number of the magnetocaloric crystallization re-annealing circulation steps used in the invention is 2-5.
Example 1:
in a clean 100ml beaker, adding 1.1g zinc acetate dihydrate, 0.28g potassium hydroxide and 1.48g sodium citrate dihydrate, adding 70ml deionized water to prepare a precursor solution, and stirring at 70 ℃ for reaction for 4 hours; pretreating foam nickel with the specification of 3cm multiplied by 3cm, removing impurities on the surface of the foam nickel by using a HCI solution with the concentration of 1mol/L, and then washing and drying for later use; then placing the treated foam nickel in a precursor solution, reacting for 6 hours under the action of an alternating magnetic field through a magnetocaloric effect, and regulating the intensity of the magnetic field to enable the reaction temperature to be 180 ℃; then taking out the foam nickel-based catalyst, washing, drying and annealing at 200 ℃; and (3) after the step of carrying out the magnetocaloric reaction and the recrystallization for 3 times, washing and drying by using deionized water to obtain the foam nickel@zinc oxide directional heteroepitaxy composite catalyst.
Example 2:
in a clean 100ml beaker, adding 0.55g zinc acetate dihydrate, 0.12g potassium hydroxide and 0.74g sodium citrate dihydrate, and adding 60ml deionized water to prepare a precursor solution, and stirring and reacting for 3 hours at 75 ℃; pretreating a nickel plate with the specification of 3cm multiplied by 3cm, removing impurities on the surface of foam nickel by using a HCI solution with the concentration of 1mol/L, and then washing and drying for later use; then placing the treated nickel plate in a precursor solution, reacting for 4 hours under the action of an alternating magnetic field through a magnetocaloric effect, and regulating the intensity of the magnetic field to ensure that the reaction temperature is 120 ℃; then, taking out the nickel-based catalyst, washing, drying and annealing at 220 ℃; and (3) after 4 times of the step of re-crystallization through the magnetocaloric reaction, washing with deionized water and drying to obtain the nickel plate @ zinc oxide directional heteroepitaxy composite catalyst.
Example 3:
in a clean 100ml beaker, adding 0.825g zinc acetate dihydrate, 0.33g potassium hydroxide and 1.48g sodium citrate dihydrate, and adding 70ml deionized water to prepare a precursor solution, and stirring and reacting for 4 hours at 70 ℃; pretreating foam iron-nickel with the specification of 3cm multiplied by 3cm, removing impurities on the surface of the foam iron-nickel by using a HCI solution with the concentration of 1mol/L, and then washing and drying for later use; then placing the treated foam iron-nickel in a precursor solution, reacting for 6 hours under the action of an alternating magnetic field through a magnetocaloric effect, and regulating the intensity of the magnetic field to enable the reaction temperature to be 200 ℃; then taking out the foam nickel-based catalyst, washing, drying and annealing at 240 ℃; and (3) after the step of carrying out the magnetocaloric reaction and the recrystallization for 3 times, washing and drying by using deionized water to obtain the foam iron-nickel@zinc oxide directional heteroepitaxy composite catalyst.
Example 4:
in a clean 100ml beaker, adding 0.55g zinc acetate dihydrate, 0.14g potassium hydroxide and 1.11g sodium citrate dihydrate, and adding 70ml deionized water to prepare a precursor solution, and stirring at 80 ℃ for reaction for 4 hours; then ferroferric oxide particles are placed in a precursor solution, stirred and reacted for 6 hours through a magnetocaloric effect under the action of an alternating magnetic field, and the intensity of the magnetic field is regulated to ensure that the reaction temperature is 180 ℃; then, taking out the foam nickel-based catalyst, filtering, washing, drying and annealing at 200 ℃; and (3) after 4 times of the steps of the magnetocaloric reaction recrystallization, filtering, washing and drying by using deionized water to obtain the ferroferric oxide@zinc oxide directional heteroepitaxy composite catalyst.
Example 5:
in a clean 100ml beaker, adding 1.1g zinc acetate dihydrate, 0.42g potassium hydroxide and 2.22g sodium citrate dihydrate, and adding 70ml deionized water to prepare a precursor solution, and stirring and reacting for 4 hours at 75 ℃; then nickel oxide particles are placed in a precursor solution and react for 6 hours through a magnetocaloric effect under the action of an alternating magnetic field, and the intensity of the magnetic field is regulated to ensure that the reaction temperature is 180 ℃; then, taking out the nickel oxide-based catalyst, filtering, washing, drying and annealing at 200 ℃; and (3) after the step of carrying out the magnetocaloric reaction and the recrystallization for 5 times, filtering, washing and drying by using deionized water to obtain the nickel oxide@zinc oxide directional heteroepitaxy composite catalyst.
Example 6:
in a clean 100ml beaker, adding 1.1g zinc acetate dihydrate, 0.28g potassium hydroxide and 1.48g sodium citrate dihydrate, adding 70ml deionized water to prepare a precursor solution, and stirring at 70 ℃ for reaction for 4 hours; then placing cobaltosic oxide particles in a precursor solution, reacting for 6 hours under the action of an alternating magnetic field through a magnetocaloric effect, and regulating the intensity of the magnetic field to enable the reaction temperature to be 240 ℃; then, taking out the cobaltosic oxide-based catalyst, filtering, washing, drying and annealing at 200 ℃; and (3) after the step of carrying out the magnetocaloric reaction recrystallization for 5 times, filtering, washing and drying by using deionized water to obtain the directional heteroepitaxy composite catalyst of the cobaltosic oxide and the zinc oxide.
Finally, it should be understood that the embodiments described herein are merely illustrative of the principles of the embodiments of the present invention; other variations are possible within the scope of the invention; thus, by way of example, and not limitation, alternative configurations of embodiments of the invention may be considered in keeping with the teachings of the invention; accordingly, the embodiments of the present invention are not limited to the embodiments explicitly described and depicted herein.
Claims (8)
1. A preparation method of a directional heteroepitaxy composite catalyst by utilizing a magnetocaloric effect is characterized in that the magnetocaloric effect generated by a magnetic substrate in an alternating magnetic field is utilized, and then crystal directional heteroepitaxy is grown on the surface of the magnetic substrate through cyclic crystallization of the magnetocaloric effect, so that the directional heteroepitaxy composite catalyst is synthesized; the preparation method comprises the following specific steps:
step (1), preparing precursor solution by adding prepared zinc acetate dihydrate, potassium hydroxide and sodium citrate dihydrate into water,
step (2), preparing a magnetic substrate, preprocessing, placing the magnetic substrate in a precursor solution, performing magnetocaloric reaction under the action of an alternating magnetic field, and enabling crystals to grow directionally on the surface of the magnetic substrate through local high temperature generated on the surface of the magnetic substrate, so as to generate a composite catalyst;
step (3), taking out the composite catalyst from the precursor solution and annealing;
and (4) cycling the steps for a plurality of times, and enabling the zinc oxide crystal to grow on the magnetic substrate in a directional heteroepitaxy manner after the composite catalyst repeatedly undergoes a magnetocaloric crystallization and re-annealing process.
2. The method for preparing a directional heteroepitaxy composite catalyst using magnetocaloric effect according to claim 1, wherein in step (1), the molar ratio of zinc acetate dihydrate to potassium hydroxide is 5: 1-2: 1, a step of; the molar ratio of zinc acetate dihydrate to sodium citrate dihydrate is 1:1 to 1:2; the water is deionized water.
3. The method for preparing a directional heteroepitaxy composite catalyst using magnetocaloric effect according to claim 1, wherein in step (1), the reaction temperature of the prepared precursor solution is 65-85 ℃ and the reaction time is 2-8 h.
4. The method for preparing a directional heteroepitaxy composite catalyst using magnetocaloric effect according to claim 1, wherein in step (2), the magnetic substrate is one of iron/cobalt/nickel-based-foam metal, magnetic metal plate and large-sized magnetic particles.
5. The method for preparing a directional heteroepitaxy composite catalyst using magnetocaloric effect according to claim 1, wherein in step (2), the frequency of the alternating magnetic field is 10 -1 ～10 5 Hz, the magnetic field intensity is 0.1-100 mT.
6. The method for preparing a directional heteroepitaxy composite catalyst using magnetocaloric effect according to claim 1, wherein in step (2), the magnetocaloric reaction time is 0.5-8 h, and the reaction temperature is 80-240 ℃.
7. The method for preparing a directional heteroepitaxy composite catalyst using magnetocaloric effect according to claim 1, wherein in step (3), the annealing temperature is 180-220 ℃ and the annealing time is 1-4 h.
8. The method for preparing a directional heteroepitaxy composite catalyst using magnetocaloric effect according to claim 1, wherein in step (4), the number of circulation steps is 2 to 5.
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| CN110230042A (en) * | 2019-06-13 | 2019-09-13 | 大连理工大学 | A kind of magnetic photonic crystal micro-sphere material and preparation method thereof |
| CN110436529A (en) * | 2019-09-08 | 2019-11-12 | 兰州大学第一医院 | A kind of Fe can be used for magnetic thermotherapy3O4The preparation method of nano-bar material |
| CN111617771A (en) * | 2020-05-20 | 2020-09-04 | 东南大学 | Preparation method of composite metal material catalyst and application of composite metal material catalyst in preparation of 5-HMF |
| CN113258003A (en) * | 2021-05-28 | 2021-08-13 | 电子科技大学 | Organic photovoltaic device preparation process based on metal nanoparticle magnetic thermal effect annealing process |
| CN113985325A (en) * | 2021-09-16 | 2022-01-28 | 彭彦莉 | Alternating magnetic field detection device based on magnetocaloric effect |
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