CN113060771B - Preparation method and application of amorphous small-size cobalt oxide loaded tantalum oxynitride - Google Patents
Preparation method and application of amorphous small-size cobalt oxide loaded tantalum oxynitride Download PDFInfo
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- CN113060771B CN113060771B CN202110263159.2A CN202110263159A CN113060771B CN 113060771 B CN113060771 B CN 113060771B CN 202110263159 A CN202110263159 A CN 202110263159A CN 113060771 B CN113060771 B CN 113060771B
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- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 53
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 53
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- 238000006862 quantum yield reaction Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 229910003071 TaON Inorganic materials 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000002256 photodeposition Methods 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- -1 salt cobalt acetylacetonate Chemical class 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0821—Oxynitrides of metals, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- 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
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Catalysts (AREA)
Abstract
The invention relates to a preparation method and application of amorphous small-size cobalt oxide loaded tantalum oxynitride. Firstly, synthesizing tantalum oxynitride (TaON) by utilizing high-temperature nitridation reaction, and then using metal organic salt cobalt acetylacetonate (Co (acac) 2 ) As a precursor, the method adopts a light deposition mode to uniformly load cobalt oxide (CoO) on the surface of tantalum oxynitride (TaON) x ) The load state is the key for improving the photocatalytic oxygen production performance of tantalum oxynitride, and the optimal oxygen production performance can reach 6120+/-342 mu mol g ‑1 h ‑1 The Apparent Quantum Yield (AQY) at 420nm wavelength was 21.2.+ -. 1.05%. The load mode of the photo-deposition metal organic salt is suitable for tantalum-based nitride, the preparation process is simple and convenient, the environment is friendly, and the prepared material system can be used as an oxygen-generating end material of a photo-catalytic full-decomposition water Z system, and has very wide application prospect in the fields of environmental science and new energy.
Description
Technical Field
The invention relates to an amorphous small-size cobalt oxide (CoO) with high-efficiency photocatalytic decomposition of water to produce oxygen x ) Preparation method and application of supported tantalum oxynitride, amorphous small-size cobalt oxide (CoO) x ) Is critical for effective improvement of material properties. The material is used as a photocatalytic oxygen generating material and has higher photocatalytic oxygen generating performance. The preparation process is simple and environment-friendly, and the prepared material system can be used as an oxygen-generating end material of a photocatalytic total-decomposition water Z system, and has very important prospects in the fields of environmental science and new energy.
Background
Currently, energy crisis and environmental problems are two important issues that need to be addressed worldwide. The direct conversion of solar energy into chemical energy by using a semiconductor photocatalysis technology is considered as one of the most promising technical concepts, and the technology has the advantages of simple process, easily available raw materials, cleanness and environmental protection, and has potential application value in the fields of environmental protection and energy. The photocatalytic water splitting reaction consists of two half reactions, namely the oxidation of water to oxygen and the reduction of water to hydrogen, which are decisive for the overall efficiency of the total splitting of water, since water oxidation is a four-electron transport process. Tantalum oxynitride (TaO) is an excellent photocatalytic oxygen generating material, and is widely focused and studied by virtue of the special advantages of relatively narrow band gap (about 2.1-2.5 eV), proper valence band position, good visible light absorption performance, good stability, no toxicity and the like.
The photocatalytic water oxidation is mainly divided into the following three steps: the semiconductor photocatalyst captures and absorbs sunlight, electrons and holes in the semiconductor material are separated and transmitted by light excitation, and the electrons and the holes migrate to the surface of the semiconductor to respectively participate in the reduction of the sacrificial agent and the oxidation of water to generate oxygen. However, tantalum oxynitride (ox) still has problems of internal charge separation, low transport efficiency, high charge recombination rate and slow water oxidation kinetics as a semiconductor material. To solve this problem, people have achieved staged results by means of element doping, promoter loading, heterojunction construction, etc. The cocatalyst loading is a simpler and effective method, and the photocatalysis performance can be greatly improved under the condition of loading a very small amount of cocatalyst. At the same time, the crystal structure, size and distribution of the cocatalyst can greatly influence the performance of the cocatalyst. At present, the photocatalytic oxygen production promoter mainly comprises IrO 2 、RuO 2 、CoO x And the like, the preparation of the cocatalyst which can greatly improve the photocatalytic oxygen production performance of the tantalum oxynitride (tantalum oxide) is necessary.
The invention uses the simple method of photo-depositing metal organic salt to load uniformly dispersed amorphous small-size oxidation on the TaON surfaceCobalt (CoO) x ) The structure can effectively improve the photocatalytic oxygen production performance of TaON. Meanwhile, the device can be applied to an oxygen generating end of the device, and the efficiency of fully decomposing water is hopefully improved greatly. The preparation method is simple and convenient, clean and environment-friendly, and has very wide application prospect in the fields of photocatalysis and photoelectrocatalysis.
Disclosure of Invention
The invention aims to provide a preparation method and application of amorphous small-size cobalt oxide (CoOx) loaded tantalum oxynitride with high-efficiency photocatalytic decomposition of water to produce oxygen, and the preparation method is simple and high in repeatability. The prepared material has excellent photocatalytic water splitting oxygen generating capacity and obvious apparent quantum yield.
In order to achieve the above purpose, the invention adopts the following technical scheme:
amorphous small-size cobalt oxide (CoO) with high-efficiency photocatalytic decomposition of water to produce oxygen x ) The preparation method of the supported tantalum oxynitride comprises the following steps:
tantalum oxide (Ta) 2 O 5 ) The powder is fully ground and then is put into a square boat, then the square boat is put into a tube furnace, and the powder is calcined for 12-15 hours at 850-950 ℃ under the ammonia atmosphere (25-45 cc/min) to obtain tantalum oxynitride (TaON) powder. The obtained tantalum oxynitride powder is added into a mixture containing a certain amount of Co (acac) 2 After fully ultrasonic dispersion, placing the mixed solution under a full-band light source for illumination for a certain time, and centrifugally drying to obtain the amorphous small-size cobalt oxide (CoOx) -loaded tantalum oxynitride.
The Co (acac) with certain content 2 Co (acac) in aqueous ethanol mixed solution 2 The mass of (a) is 5mg-70mg (preferably 10 mg), the volume of water is 20-50mL, and the volume of ethanol is 10-30mL. The vacuum drying is carried out in a vacuum oven at 40-90 ℃ (preferably 60 ℃) for 6-14h (preferably 12 h).
The sufficient ultrasonic dispersion requires the mixed solution to be subjected to ultrasonic treatment for more than 20 minutes.
The xenon lamp with the illumination time of 300W under the full-wave band light source illuminates for 0.5-3.5h (preferably 10 mg).
The invention also provides an amorphous small-sizeCobalt oxide (CoO) x ) The tantalum oxynitride is used for photocatalytic decomposition of water to produce oxygen.
The application method comprises the following steps: 20-100mg (preferably 25 mg) of amorphous small-size cobalt oxide (CoO) x ) Tantalum oxynitride loaded powder is ultrasonically dispersed in 30-150mL (preferably 50 mL) of 0.015-0.1M (preferably 0.05M) AgNO 3 In the aqueous solution, a reaction kettle containing the reaction solution is connected to a glass closed circulation system (CEL-SPH 2N, CEAULIGHT, china), and the whole system is vacuumized to be minus 0.1MPa. The test condition is that a 300W xenon lamp is used as a light source, a lambda > 420nm optical filter is adopted, the test temperature of the solution is kept at 8-15 ℃, samples are sampled every 30min, and the response value of oxygen is detected by using a chromatograph.
Other conditions were kept unchanged during the AQY test, and the filters were replaced with monochromatic light at λ=375, 420, 475, 520, 550nm and 630 nm. The oxygen generating performance under visible light (lambda > 420 nm) is 5778-6462 mu mol g -1 h -1 AQY is 26.55% at λ=375 nm; λ=420 nm, AQY is 21.17%; λ=475 nm, AQY is 16.34%; λ=520 nm, AQY is 6.05%; λ=550 nm, AQY is 4.31%; at λ=630 nm, AQY is 3.33%.
The invention has the beneficial effects that:
(1) The method for synthesizing tantalum oxynitride by one step of high-temperature nitridation and electrodepositing metal organic salt is characterized in that uniformly dispersed amorphous small-size cobalt oxide (CoOx) is loaded on the surface of the tantalum oxynitride, the synthesis operation is simple and convenient, the condition is mild, the purity of the target product is high, the repeatability is good, and the large-scale synthesis can be realized;
(2) The amorphous small-size cobalt oxide (CoOx) loaded tantalum oxynitride is used as a photocatalytic decomposition water-oxygen generating material, and the result shows that the material has very excellent photocatalytic decomposition water-oxygen generating performance, and the optimal oxygen generating performance is 6120+/-342 mu mol g -1 h -1 Apparent quantum yield at 420nm wavelength (AQY) was 21.17%;
(3) In the preparation process, all reagents are commercial products and do not need further treatment.
Drawings
FIG. 1 is a transmission electron micrograph of the product prepared in example 1 and a distribution of elemental planes of the local crystals;
FIG. 2 is the oxygen production rate obtained after 1 hour of testing the product prepared in example 1 as a photocatalytic oxygen producing material;
FIG. 3 is a graph of the UV-vis spectrum of the product prepared in example 1 and its measured AQY values for monochromatic filters of different wavelengths;
FIG. 4 is an X-ray photoelectron spectrum and K-space spectrum of cobalt in the product prepared in example 1;
FIG. 5 is a photo-deposited divalent acetylacetonate Co (acac) 2 Photo-depositing trivalent cobalt acetylacetonate Co (acac) 3 And the average oxygen production rate obtained by catalyzing water to decompose for 1 hour in the light by using the comparison sample as an oxygen production catalyst;
FIG. 6 is a graph of photocatalytic oxygen production performance of materials at different photodecomposition times;
FIG. 7 is Co (acac) 2 Photo-deposition as a precursor to amorphous small-size cobalt oxide (CoO) x ) Tantalum oxynitride loaded UV-vis spectra and measured values of AQY under monochromatic filters of different wavelengths;
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to the drawings and examples, but should not be construed as limiting the scope of the invention.
"Range" is disclosed herein in the form of lower and upper limits. There may be one or more lower limits and one or more upper limits, respectively. The given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular ranges. All ranges that can be defined in this way are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for specific parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum ranges 3,4 and 5 are listed, the following ranges are all contemplated: 1-2, 1-4, 1-5, 2-3, 2-4 and 2-5.
In the present invention, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values.
In the present invention, all the embodiments mentioned herein and the preferred embodiments may be combined with each other to form new technical solutions, if not specifically described.
In the present invention, all technical features mentioned herein and preferred features may be combined with each other to form new technical solutions, if not specifically stated.
Preferred embodiments of the present invention will be specifically described below with reference to specific embodiments, but it should be understood that reasonable variations, modifications and combinations of these embodiments can be made by those skilled in the art without departing from the scope of the present invention as defined in the appended claims, thereby obtaining new embodiments, and these new embodiments obtained by variations, modifications and combinations are also included in the scope of protection of the present invention.
Example 1
Step one, amorphous small-size cobalt oxide (CoO) x ) Preparation of supported tantalum oxynitride
Firstly, synthesizing tantalum oxynitride TaON: 800mg of tantalum oxide (Ta 2 O 5 ) The powder was sufficiently ground and placed in a ark, after which the ark was placed in a tube furnace and calcined at 900℃for 12 hours under an ammonia atmosphere (35 cc/min) to obtain tantalum oxynitride (TaON) powder. The tantalum oxynitride powder thus obtained was added to a mixed solution composed of 10mL of ethanol and 30mL of water, and 5mg of cobalt acetylacetonate (Co (acac)) was added to the mixed solution 2 ) After ultrasonic dispersion for 30min, the mixed solution is placed under a full-wave band light source provided by a 300W xenon lamp (CEL-HXBF 300) to be irradiated for 30min, the irradiated mixed solution is collected and washed three times by deionized water, and the mixed solution is dried in vacuum at 60 ℃ overnight to obtain cobalt oxide-loaded tantalum oxynitride.
FIG. 1 shows the prepared amorphous small-sized cobalt oxide (CoO x ) Tantalum oxynitride loaded X-ray diffraction pictures, samples with different precursors and different precursor amounts subjected to photo-deposition show the same peak shapeAnd peak position.
FIG. 2 is a transmission electron micrograph of the prepared amorphous small-sized cobalt oxide (CoOx) -loaded tantalum oxynitride and a partial elemental plane distribution of the crystal, showing that the uniformly dispersed amorphous small-sized cobalt oxide (CoO) x ) Is loaded on the surface of the tantalum oxynitride material.
FIG. 3 is Co (acac) 2 Photo-deposition as a precursor to amorphous small-size cobalt oxide (CoO) x ) The photoelectron spectrum of the supported tantalum oxynitride, FIG. 4 is a close-up spectrum of the corresponding X-ray absorbing fine structure, and the comprehensive analysis of FIGS. 3 and 4 advantageously demonstrates that the cobalt oxide (CoO) has a small crystal size x ) The valence state of Co is positive bivalent.
Step two, performance characterization test
Amorphous small-sized cobalt oxide (CoO) x ) The photodecomposition of oxygen by supporting the tantalum oxynitride photocatalyst was performed in a glass gas-closed circulation system (CEL-SPH 2N, CEAULIGHT, china) with a top-irradiation reactor. 25mg of photocatalyst was dispersed in 50mL of 0.025M AgNO 3 In aqueous solution, the reactor containing the above solution was placed in an ultrasonic water bath for 5 minutes to disperse before the reaction, and stirring was continued during the test. During the test, the reactant solution was maintained at 10 ℃ by cooling water. Prior to irradiation, the reaction system was evacuated several times to remove the internal air, maintaining the internal pressure at-0.1 MPa. A300W xenon lamp (CEL-HXBF 300) equipped with an ultraviolet cut filter was used to provide visible light with lambda > 420 nm. Determination of O produced in the gas phase by an on-line gas chromatograph (GC 2060, TCD detector and Ar Carrier) 2 Is a combination of the amounts of (a) and (b). In addition, the apparent quantum yield was tested using a 300W xenon lamp with monochromatic light (λ=375, 420, 475, 520, 550, 630 nm) as the light source, the other test conditions remained unchanged.
FIG. 5 is a photo-deposited divalent acetylacetonate Co (acac) 2 Photo-depositing trivalent cobalt acetylacetonate Co (acac) 3 And a comparative sample as an oxygen-generating catalyst for catalyzing water decomposition 1 in lightAverage oxygen production rate obtained in hours, and according to chromatographic response value and combined with oxygen calibration result, electrodepositing Co (acac) 2 The obtained amorphous small-sized cobalt oxide (CoO x ) The tantalum oxynitride loaded has the best performance, and the oxygen production rate is 6117+/-342 mu mol g -1 h -1 Proved by amorphous small-sized cobalt oxide (CoO x ) Is critical for performance improvement.
Fig. 6 is a graph of photocatalytic oxygen production performance of materials at different photo deposition times. 5mg Co (acac) 2 The photocatalytic oxygen production performance as a precursor increases rapidly and then decreases slowly with the increase of the photo-deposition time. 5mg Co (acac) 3 The photocatalytic oxygen production performance as a precursor increases with the time of the photo-deposition.
FIG. 7 is Co (acac) 2 Photo-deposition as a precursor to amorphous small-size cobalt oxide (CoO) x ) The UV-vis spectrum of the supported tantalum oxynitride and its AQY values measured with monochromatic filters of different wavelengths, show that it still has an absorption at 630nm and a higher AQY at 420nm of 21.17+ -1.05%.
Example 2
The procedure of example 1 was repeated except that the tantalum oxynitride powder obtained was added to a powder containing a certain amount of Co (acac) 2 After fully ultrasonic dispersion, the mixed solution is placed under a visible light source to be irradiated for a certain time, and the amorphous cobalt oxide (CoO) with small size is obtained after centrifugal drying x ) Supported tantalum oxynitride.
Example 3
The procedure of example 1 was repeated except that the tantalum oxynitride powder obtained was added to a powder containing a certain amount of Co (acac) 2 After fully ultrasonic dispersion, placing the mixed solution under a near infrared light source for illumination for a certain time, and centrifugally drying to obtain amorphous small-size cobalt oxide (CoO) x ) Supported tantalum oxynitride.
Example 4
The procedure of example 1 was repeated except that the tantalum oxynitride powder obtained was added to a powder containing a certain amount of cobalt nitrate Co (NO 3 ) 2 After fully ultrasonic dispersion, the mixed solution is placed under a visible light source to be irradiated for a certain time, and the amorphous cobalt oxide (CoO) with small size is obtained after centrifugal drying x ) Supported tantalum oxynitride.
Example 5
The procedure of example 1 was repeated except that the tantalum oxynitride powder obtained was added to a mixed solution of aqueous ethanol containing a certain amount of cobalt phthalocyanine, and after sufficient ultrasonic dispersion, the mixed solution was subjected to illumination under a visible light source for a certain period of time, and centrifugal drying was performed to obtain amorphous small-sized cobalt oxide (CoO) x ) Supported tantalum oxynitride.
Example 6
The procedure of example 1 was repeated except that the tantalum oxynitride powder obtained was added to a powder containing a certain amount of cobalt chloride CoCl 2 After fully ultrasonic dispersion, the mixed solution is placed under a visible light source to be irradiated for a certain time, and the amorphous cobalt oxide (CoO) with small size is obtained after centrifugal drying x ) Supported tantalum oxynitride.
Example 7
The procedure of example 1 is repeated, with other common tantalum-based nitrides and tantalum-based titanium compounds such as (Ta 3 N 5 ，LaTiO 2 N，Sr 2 Ta 2 O 7-x N x ，Zr x Ta 1-x O 1+x N 1-x ，LaTaON 2 ，CaTaO 2 N，BaTaO 2 N, etc.) can be used to achieve a substantial improvement in photocatalytic oxygen production performance.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (4)
1. The preparation method of the amorphous small-size cobalt oxide loaded tantalum oxynitride is characterized by comprising the following steps of:
tantalum oxide Ta 2 O 5 Fully grinding the powder, placing into a square boat, placing the square boat into a tubular furnace, and placing under ammonia atmosphere of 25-45cc/minCalcining at 850-950 ℃ for 12-15h to obtain tantalum oxynitride TaON powder; the obtained tantalum oxynitride powder is added into a mixture containing a certain amount of Co (acac) 2 After fully ultrasonic dispersion, placing the mixed solution under a full-band light source to irradiate for a certain time, and centrifugally drying to obtain the amorphous small-size cobalt oxide CoO x Supported tantalum oxynitride; said composition contains a certain amount of Co (acac) 2 Co (acac) in aqueous ethanol mixed solution 2 The mass of the water-based oil is 5mg-70mg, the volume of water is 20-50mL, and the volume of ethanol is 10-30mL; the drying is that the materials are dried for 6 to 14 hours in a vacuum oven at the temperature of 40 to 90 ℃; the sufficient ultrasonic dispersion requires the mixed solution to be subjected to ultrasonic treatment for more than 20 minutes; and the xenon lamp with the illumination time of 300W under the full-wave band light source illuminates for 0.5-3.5 hours.
2. The use of the amorphous small-sized cobalt oxide-supported tantalum oxynitride prepared by the preparation method according to claim 1, wherein the prepared amorphous small-sized cobalt oxide-supported tantalum oxynitride is applied to photocatalytic decomposition of water to produce oxygen.
3. The use according to claim 2, characterized in that the application method is as follows: ultrasonically dispersing 20-150mg of amorphous small-size cobalt oxide loaded tantalum oxynitride powder in 30-150mL of 0.015-0.1M AgNO 3 In the aqueous solution, connecting a reaction kettle containing the reaction solution into a glass closed circulation system, and vacuumizing to the whole system of-0.1 MPa; a xenon lamp with a test condition of 300W is used as a light source and lambda is adopted>The filter at 420nm is used, the temperature of the solution is kept at 8-15 ℃, samples are sampled every 30min, and the response value of oxygen is detected by using a chromatograph.
4. The use according to claim 3, characterized in that λ under visible light when tested for apparent quantum yield AQY>The oxygen generating performance at 420nm is 5778-6462 mu mol g -1 h -1 Other conditions remained unchanged, the filter was changed to monochromatic light of λ=375, 420, 475, 520, 550nm and 630nm, and AQY was 26.55% when λ=375 nm; AQY is 21.17% when λ=420 nm; when λ=475 nm,AQY is 16.34%; AQY is 6.05% when λ=520 nm; AQY is 4.31% when λ=550 nm; AQY is 3.33% when λ=630 nm.
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| CN110116015A (en) * | 2018-02-06 | 2019-08-13 | 西安交通大学 | Complete photochemical catalyst for decomposing water and its preparation method and application, photocatalysis decompose the reaction method and catalytic mixing liquid of water completely |
| CN110605138A (en) * | 2019-10-09 | 2019-12-24 | 江苏泷膜环境科技有限公司 | Preparation method and application of tantalum oxygen nitrogen/foamed nickel photocatalytic contact oxide film |
| CN110801836A (en) * | 2019-10-18 | 2020-02-18 | 华东理工大学 | Rhodium-loaded bismuth vanadate with high-efficiency photocatalytic aquatic oxygen decomposition performance, and preparation method and application thereof |
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| CN110116015A (en) * | 2018-02-06 | 2019-08-13 | 西安交通大学 | Complete photochemical catalyst for decomposing water and its preparation method and application, photocatalysis decompose the reaction method and catalytic mixing liquid of water completely |
| CN110605138A (en) * | 2019-10-09 | 2019-12-24 | 江苏泷膜环境科技有限公司 | Preparation method and application of tantalum oxygen nitrogen/foamed nickel photocatalytic contact oxide film |
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