CN113663672B - Cobalt oxide photocatalytic material with high photoelectrocatalytic activity and preparation method thereof - Google Patents
Cobalt oxide photocatalytic material with high photoelectrocatalytic activity and preparation method thereof Download PDFInfo
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- cobalt oxide
- sodium hydroxide
- cobalt oxalate
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 34
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 20
- 230000000694 effects Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 26
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011858 nanopowder Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000000120 microwave digestion Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910002451 CoOx Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a cobalt oxide photocatalytic material with high photoelectrocatalytic activity and a preparation method thereof. The method is to prepare a precursor by using a cobalt oxalate aqueous solution and a sodium hydroxide aqueous solution, and prepare the cobalt oxide by microwave hydrothermal treatment, drying and high-temperature treatment. The invention provides a novel synthesis method of cobalt oxide powder with controllable grain size. The method can obviously improve the photocatalytic reaction activity of the material. The cobalt oxide powder produced by the method is expected to be further applied to the field of photocatalysis. The production method has low cost and simple and convenient synthesis process, can be applied to mass production, and effectively saves the production cost. The cobalt oxide powder prepared by the invention has excellent photoelectrocatalysis activity and has a large commercialization prospect.
Description
Technical Field
The invention belongs to the field of photocatalytic water splitting, and particularly relates to cobalt oxide powder with high photocatalytic activity and a preparation method thereof.
Background
In recent years, a great deal of research has shown that cobalt-based oxides have excellent electrocatalytic water decomposition properties, and electrons can be efficiently transferred between the surface of a cobalt-based catalyst and water molecules via cobalt atoms. Meanwhile, cobalt compounds are also applied to research of hydrogen production by photocatalytic decomposition of seawater, such as Co 3 O 4 Co-Pi, etc. Cobalt oxide belongs to a semiconductor, but has very high carrier mobility, and is a semiconductor photocatalytic material with potential. Due to different crystals of the photocatalystThe atomic arrangement of the surface can have important influence on the adsorption and desorption properties of reactants and the electron transport properties between a photo-generated carrier and the reactants, so that the photocatalyst particles are exposed to a crystal face with high reactivity through a proper synthesis method, and the photocatalytic reaction can be carried out at a higher speed, which is a research hot spot in the field at present.
It has been reported that the water-splitting active component of the cobalt-based homogeneous catalyst is CoOx nanoparticles after degradation of the homogeneous catalyst, so that downsizing of cobalt oxide to the nanoscale is key to the photocatalytic activity. The development of the cobalt-based inorganic catalyst can not only achieve the aim of improving the water decomposition reaction performance, but also overcome the defects that the homogeneous catalyst is difficult to recover and has severe requirements on the micro-environment of the catalytic reaction. The main synthesis methods at present are high-temperature heating, femtosecond laser ablation and the like. The cobalt oxide synthesized by the method can generate overlarge particle diameter, is easy to agglomerate in the reaction process and deposit Mg in seawater 2+ 、Ca 2+ Ion and the like, thereby causing the stability of the photocatalyst to be reduced and shortening the service life. Therefore, the design and synthesis of high-efficiency stable photocatalytic materials suitable for decomposing seawater hydrogen are still needed.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the cobalt oxide for photocatalysis and the preparation method thereof, and the cobalt oxide prepared by the method has stronger photoelectrocatalysis activity.
To achieve the above object, the present invention provides a method for preparing a cobalt oxide photocatalytic material having high photocatalytic activity, wherein the method comprises preparing a precursor (i.e., intermediate Co (OH)) from an aqueous solution of cobalt oxalate and an aqueous solution of sodium hydroxide 2 ) The cobalt oxide is prepared through microwave hydrothermal treatment, drying and high-temperature treatment.
According to a specific embodiment of the present invention, the above method may comprise the steps of:
dissolving cobalt oxalate in deionized water to obtain a cobalt oxalate aqueous solution, dripping a sodium hydroxide aqueous solution into the cobalt oxalate aqueous solution in a water bath environment, and preserving heat for a proper time after the dripping is completed to obtain a precursor;
carrying out microwave hydrothermal treatment on the precursor to obtain a suspension;
separating, washing and drying the suspension to obtain solid powder;
and carrying out high-temperature treatment on the solid powder to obtain the cobaltous oxide nano powder.
According to a specific embodiment of the invention, in the cobalt oxalate aqueous solution, the mass ratio of the cobalt oxalate to deionized water is preferably 0.01-0.03:1.
According to a specific embodiment of the present invention, in the cobalt oxalate aqueous solution, the mass of the cobalt oxalate may be controlled to be 0.1g to 1.5g, and the volume of the deionized water may be controlled to be 5ml to 100ml.
According to a specific embodiment of the present invention, the concentration of the aqueous sodium hydroxide solution is preferably 1 to 10mol/L.
According to a specific embodiment of the present invention, the volume of the aqueous sodium hydroxide solution may be controlled to be 1-20ml.
According to a specific embodiment of the present invention, in order to ensure that sodium hydroxide can sufficiently oxidize cobalt ions in cobalt oxalate, the mass ratio of sodium hydroxide to cobalt oxalate is preferably not less than 0.2:1. the mass of sodium hydroxide and cobalt oxalate refers to the mass of pure sodium hydroxide and cobalt oxalate, and not the mass of aqueous solution thereof.
According to a specific embodiment of the invention, during the process of dropwise adding the sodium hydroxide aqueous solution, the solution is obviously and slowly discolored, the color is changed from colorless to pink, and finally, the color is changed into reddish brown, and each titration is slowly performed after the color is stable and unchanged. The temperature of the water bath can be controlled to be 50-80 ℃. The incubation time after the completion of the dropwise addition of the aqueous sodium hydroxide solution can be controlled to 10 minutes or more to ensure that the reaction proceeds sufficiently, and from the viewpoint of appearance, the reaction proceeds until the solution turns from pink to dark brown and the color does not become deep with the dropwise addition of the aqueous sodium hydroxide solution.
According to a specific embodiment of the present invention, the microwave hydrothermal temperature may be controlled to 150-220 ℃ and the time may be controlled to 10-60 minutes (preferably about 30 minutes). The power of the microwaves is controlled to be not lower than 1000W. Microwave hydrothermal may be performed in a microwave digestion tank.
According to an embodiment of the invention, the suspension may be washed several times with deionized water and ethanol after separation, preferably by vacuum drying.
According to a specific embodiment of the present invention, the temperature of the high temperature treatment is preferably 800 ℃ to 900 ℃; more preferably, the temperature rising rate is 1-10 ℃/min, and the heat preservation time is 0.5-5h. The above-mentioned high-temperature treatment is preferably performed in a nitrogen atmosphere or an inert atmosphere.
The method provided by the invention adopts a microwave solvothermal-annealing two-step method, and cobalt oxalate reacts with sodium hydroxide to generate a new precursor at a certain temperature; then carrying out microwave hydrothermal treatment, and decomposing the precursor into an intermediate product cobalt hydroxide; after the dry powder is obtained, it is subjected to a high temperature treatment in a protective atmosphere (e.g., nitrogen or inert gas atmosphere) to finally reduce the intermediate product to cobalt oxide.
The invention also provides a cobalt oxide photocatalytic material with high photoelectrocatalytic activity, which is prepared by the method. The cobaltous oxide is a nano material and is in powder shape, and the size of the cobaltous oxide is 50nm-300nm.
The invention provides a novel synthesis method of cobalt oxide powder with controllable grain size. The method can obviously improve the photocatalytic reaction activity of the material. The cobalt oxide powder produced by the method is expected to be further applied to the field of photocatalysis. The water splitting performance of the cobalt oxide powder applied to solar drive is verified, hydrogen obtained in the reaction can replace fossil fuel, and an important way is provided for solving the energy crisis and the environmental pollution problem. Meanwhile, the production method has low cost and simple and convenient synthesis process, can be applied to mass production, and effectively saves the production cost.
The cobalt oxide powder prepared by the invention has excellent photoelectrocatalysis activity and has a large commercialization prospect.
Drawings
Fig. 1 is an SEM image and a particle size distribution result image of the cobalt oxide photocatalytic material prepared in example 1.
Fig. 2 is a schematic view of the powder of the cobalt oxide photocatalytic material prepared in example 1.
Fig. 3 is a graph showing the photocurrent and time results of photocatalytic water splitting of the photocatalytic material prepared in example 1.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a preparation method of a cobalt oxide photocatalytic material with high photoelectrocatalytic activity, which comprises the following steps:
(1) 0.7322g of cobalt oxalate is dissolved in 42.5mL of deionized water to obtain cobalt oxalate aqueous solution, 7.5mL of sodium hydroxide aqueous solution with concentration of 5mol/L at 80 ℃ in water bath is dripped, and the water bath at 80 ℃ is maintained for 10 minutes to obtain a precursor;
(2) Putting the precursor into a microwave digestion tank, and performing microwave hydrothermal treatment at 200 ℃ for 20 minutes to obtain a suspension intermediate;
(3) And separating the obtained suspension, respectively washing with deionized water and ethanol for several times, and drying in a vacuum environment to obtain solid powder.
(4) The solid powder was transferred to nitrogen atmosphere and heated at 900 c to obtain the final product cobalt oxide nanopowder (as shown in fig. 2) with a size distribution of 50-250nm.
Fig. 1 is an SEM image and a particle size distribution result image of the cobalt oxide photocatalytic material prepared in this example.
Photocatalytic activity verification test:
under a three-electrode system, the photocatalytic material is subjected to activity test, specifically according to the following manner:
the photocatalytic performance is carried out in a three-electrode electrochemical workstation: the cobalt oxide powder is adhered to the surface of FTO glass by a sol-gel method to serve as a working electrode, a platinum sheet electrode serves as a counter electrode, and silver/silver chloride electricity is used as a counter electrodeThe electrode is used as a reference electrode, and 0.5M sodium sulfate is used as electrolyte; a bias of 1.23V under the reversible hydrogen electrode (0.68V for the corresponding silver/silver chloride electrode calculated from the nernst equation) was added to the electrode system; AM1.5 by a timer chopper, energy density 100mW/cm 2 The current density curve of the catalytic water decomposition of the cobalt oxide powder under the illumination and no light is obtained by the irradiation of the simulated sunlight light source.
Fig. 3 is a graph showing the photocurrent and time results of photocatalytic water splitting of the photocatalytic material prepared in example 1. Table 1 shows the results of the test of the photocatalytic performance of the photocatalytic material prepared in example 1 and the results of the photocatalytic performance of CoO powder prepared by the conventional method.
TABLE 1
As can be seen from the contents of fig. 1, 2 and table 1: the cobalt oxide photocatalytic material prepared by the invention is a nano material and has good photocatalytic performance.
Claims (10)
1. The preparation method of the cobalt oxide photocatalytic material with high photoelectrocatalytic activity comprises the steps of preparing a precursor from a cobalt oxalate aqueous solution and a sodium hydroxide aqueous solution, and preparing the cobalt oxide through microwave hydrothermal treatment, drying and high-temperature treatment; the mass ratio of the sodium hydroxide to the cobalt oxalate is not less than 0.2:1, a step of; the temperature of the microwave hydrothermal reaction is 150-220 ℃, the time is 10-60 minutes, and the power of the microwaves is not lower than 1000W; the temperature of the high-temperature treatment is 800-900 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 0.5-5h; the high temperature treatment is performed in a nitrogen atmosphere or an inert atmosphere.
2. The method according to claim 1, wherein the method comprises the steps of:
dissolving cobalt oxalate in deionized water to obtain a cobalt oxalate aqueous solution, dripping a sodium hydroxide aqueous solution into the cobalt oxalate aqueous solution in a water bath environment, and preserving heat after the dripping is completed to obtain a precursor;
carrying out microwave hydrothermal treatment on the precursor to obtain a suspension;
separating, washing and drying the suspension to obtain solid powder;
and carrying out high-temperature treatment on the solid powder to obtain the cobaltous oxide nano powder.
3. The method according to claim 1 or 2, wherein the mass ratio of cobalt oxalate to deionized water in the aqueous cobalt oxalate solution is 0.01-0.03:1.
4. A method according to claim 3, wherein the mass of the cobalt oxalate in the aqueous cobalt oxalate solution is 0.1g-1.5g, and the volume of deionized water is 5-100mL.
5. The method according to claim 1, 2 or 4, wherein the concentration of the aqueous sodium hydroxide solution is 1-10mol/L.
6. A process according to claim 3, wherein the aqueous sodium hydroxide solution has a concentration of 1-10mol/L.
7. The method according to claim 5, wherein the volume of the aqueous sodium hydroxide solution is 1-20mL.
8. The method according to claim 6, wherein the volume of the aqueous sodium hydroxide solution is 1-20mL.
9. The method of claim 2, wherein the water bath has a temperature of 50-80 ℃; the heat preservation time is more than 10 minutes.
10. A cobalt oxide photocatalytic material having high photocatalytic activity, which is prepared by the method according to any one of claims 1 to 9; the cobalt oxide is a nano material and is in powder shape, and the size of the cobalt oxide is 50nm-300nm.
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