CN113800483B - Nitrogen oxide nanosheet and preparation method thereof, photocatalyst and photocatalytic antibacterial agent - Google Patents
Nitrogen oxide nanosheet and preparation method thereof, photocatalyst and photocatalytic antibacterial agent Download PDFInfo
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- CN113800483B CN113800483B CN202111075195.2A CN202111075195A CN113800483B CN 113800483 B CN113800483 B CN 113800483B CN 202111075195 A CN202111075195 A CN 202111075195A CN 113800483 B CN113800483 B CN 113800483B
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 239000002135 nanosheet Substances 0.000 title claims abstract description 146
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 17
- 239000003242 anti bacterial agent Substances 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 40
- 239000013078 crystal Substances 0.000 claims abstract description 34
- 238000005121 nitriding Methods 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 58
- 239000012071 phase Substances 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002064 nanoplatelet Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 claims description 4
- 239000002055 nanoplate Substances 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012445 acidic reagent Substances 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 57
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 13
- 229910017604 nitric acid Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000002243 precursor Substances 0.000 description 7
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000010130 dispersion processing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
-
- 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
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- B01J35/23—
-
- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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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
Abstract
The application relates to the technical field of photocatalytic materials, and provides a nitrogen oxide nanosheet, a preparation method thereof, a photocatalyst and a photocatalytic antibacterial agent, wherein the layered oxide contains volatile metal elements; carrying out stripping treatment on the layered oxide along the [001] crystalline phase direction of the layered oxide to obtain an oxide nanosheet; and nitriding the oxide nanosheet to obtain the nitrogen oxide nanosheet. The ultrathin flaky shape obtained by stripping the layered oxide is convenient for photo-generated charges to rapidly move to the surface, so that the charge separation efficiency is remarkably improved, and the photocatalytic water decomposition activity of the nitrogen oxide nanosheet is effectively improved; in addition, volatile metal elements contained in the oxide nanosheets volatilize from the surfaces of the oxide nanosheets in the nitriding treatment process, and the rest elements are directionally converted into the oxynitride nanosheets in the ammonia atmosphere, so that the problem that the crystal face of the traditional oxynitride only exposes the low-activity crystal face is solved while the original flaky shape is kept.
Description
Technical Field
The application belongs to the technical field of photocatalyst materials, and particularly relates to a nitrogen oxide nanosheet, a preparation method of the nitrogen oxide nanosheet, a photocatalyst and a photocatalytic antibacterial agent.
Background
At present, the thermal nitridation method is mainly adopted for preparing the nitrogen oxide, namely ammonia gas continuously passes through the oxide for more than 10 hours under the condition of 1173-1373K. However, since Nb has a higher electronegativity than Ta, a large amount of reduced Nb is easily generated during the thermal nitridation process 4+ Or Nb 3+ And the Nb species with a low valence state can be used as an electron-hole recombination center to block the transmission and reaction of photo-generated charges, thereby seriously influencing the photocatalytic water splitting activity.
Therefore, the existing preparation of the narrow-band nitrogen oxide has the problems that the nitrogen oxide crystal only exposes a low-activity crystal face in the nitriding process, a large amount of reduced Nb species are easily generated, the activity in photocatalytic water decomposition is seriously influenced, and the like.
Disclosure of Invention
The application aims to provide a nitrogen oxide nanosheet and a preparation method and application thereof, and aims to solve the problem that in the existing preparation of narrow-band nitrogen oxide, the activity of the nitrogen oxide crystal in photocatalytic water decomposition is seriously influenced because the nitrogen oxide crystal only exposes a low-activity crystal face in the nitridation process.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a nitrogen oxide nanosheet, the method comprising the steps of:
preparing a layered oxide, wherein the layered oxide contains a volatile metal element;
carrying out stripping treatment on the layered oxide along the [001] crystalline phase direction of the layered oxide to obtain an oxide nanosheet;
and nitriding the oxide nanosheet to obtain the nitrogen oxide nanosheet.
According to the preparation method of the nitrogen oxide nanosheet, the layered oxide is stripped to obtain the ultrathin flaky shape, so that the ultrathin flaky shape is convenient for photo-generated charges to rapidly move to the surface, the charge separation efficiency is obviously improved, and the photocatalytic water decomposition activity of the nitrogen oxide nanosheet is effectively improved; volatile metal elements are doped in the layered oxide, the volatile metal elements are volatilized from the surface of the layered oxide in the nitriding process, the rest elements are directionally and quickly converted into the nitrogen oxide nanosheets in the ammonia atmosphere, the original flaky morphology is reserved, and the problem that only a low-activity crystal face of the oxide crystal face is exposed in the traditional nitriding process is solved.
In a second aspect, the present application provides a nitroxide nanoplate. The nitrogen oxide nanosheet comprises the nitrogen oxide nanosheet prepared by the preparation method.
The nitrogen oxide nanosheet provided by the second aspect of the application has broad spectrum capture capability and can be used for photocatalysts and anti-photocatalytic antibacterial agents. In a third aspect, the present application provides a photocatalyst comprising the above-described oxynitride nanoplatelets.
The photocatalyst provided by the third aspect of the application comprises the nitrogen oxide nanosheets, so that when the photocatalyst is used for photocatalytic hydrogen production reaction, the wide-spectrum capture capacity of the nitrogen oxide nanosheets is utilized, visible light can be responded, photo-generated charges are generated, the charge separation efficiency is enhanced through the surface-modified cocatalyst, the photocatalytic activity can be improved, and the activity of photocatalytic water decomposition for hydrogen evolution and oxygen evolution is further improved.
In a fourth aspect, the present application provides a photocatalytic antimicrobial agent comprising the nitrogen oxide nanosheets described above.
The photocatalytic antibacterial agent provided by the fourth aspect of the application comprises the nitrogen oxide nanosheet, so that the photocatalytic antibacterial agent can effectively activate oxygen molecules when being used for photocatalytic antibacterial, and generates a bactericidal active substance (such as singlet oxygen) to play a role in antibacterial and disinfection under visible light.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing a nitrogen oxide nanosheet provided in an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a alone, A and B together, and B alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In this application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the foregoing processes do not imply an execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not limit the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the specification of the embodiments of the present application may not only refer to the specific content of each component, but also refer to the proportional relationship of the weight of each component, and therefore, the proportional enlargement or reduction of the content of the related components according to the specification of the embodiments of the present application is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The embodiment of the application provides a preparation method of a nitrogen oxide nanosheet, which specifically comprises the following steps:
s01: preparing a layered oxide, wherein the layered oxide contains a volatile metal element;
s02: stripping the layered oxide along the [001] crystalline phase direction of the layered oxide to obtain an oxide nanosheet;
s03: and nitriding the oxide nanosheets to obtain the nitrogen oxide nanosheets.
According to the preparation method of the nitrogen oxide nanosheet, the layered oxide containing the volatile metal elements is prepared, the volatile metal elements can volatilize from the surface of the layered oxide in the nitriding process, the rest elements are quickly converted into the nitrogen oxide nanosheet along the [010] crystal phase direction in the ammonia atmosphere, the original flaky morphology is reserved, and the problem that only a low-activity crystal face is exposed on the crystal face of the oxide in the traditional nitriding process is solved; in addition, the layered oxide is stripped along the [001] crystalline phase direction of the layered oxide, so that ultrathin oxide nanosheets can be obtained, the ultrathin flaky shape is convenient for photo-generated charges to rapidly move to the surface, the charge separation efficiency is obviously improved, and the photocatalytic water splitting activity of the nitrogen oxide nanosheets is effectively improved.
In step S01, the layered oxide is a precursor of a nitrogen oxide nanosheet. In some embodiments, preparing the layered oxide specifically includes: mixing various source compounds of the oxide with a fluxing agent in an oxygen environment, melting, cooling, and purifying to obtain the layered oxide, wherein the fluxing agent comprises sodium chloride, potassium chloride, lithium chloride, cesium chloride, magnesium chloride, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, magnesium hydroxide and Na 2 CO 3 But is not limited thereto. In a specific embodiment, the flux may be sodium hydroxide and potassium hydroxide, and the flux may also be sodium hydroxide. The fluxing agent of the embodiment contains volatile metal elements, so that the volatile metal elements can be removed from the surface of the oxide sheet in the nitridation process of the oxide sheetThe rest of atoms are volatilized under the atmosphere of ammonia gas [010]]The direction is quickly converted into the nitrogen oxide nanosheet, and the original flaky shape is kept.
In some embodiments, the volatile metal element comprises at least one of an alkali metal and an alkaline earth metal element.
In some embodiments, the volatile metal element includes at least one of lithium, sodium, potassium, cesium, magnesium, but is not limited thereto. The volatile metal element is present in the form of ions in the layered oxide. In particular embodiments, the alkali metal may include, but is not limited to, at least one of lithium, sodium, potassium, cesium, and magnesium. The layered oxide contains volatile metal elements, so that the volatile metal elements such as K and Na volatilize from the surface of the oxide nanosheet in the nitridation treatment process of the oxide nanosheet, and the rest atoms are quickly converted into the nitrogen oxide nanosheet along the [010] direction in the ammonia atmosphere, and the original flaky shape is maintained.
In particular embodiments, the layered oxide comprises LaKNaTaO 5 、LaKNaNbO 5 、(Na 1/4 Ba 3/4 )(Zn 1/4 Ta 3/4 )O 3 、KLaTa 2 O 7 And KCa 2 Nb 3 O 10 But is not limited thereto. In a specific embodiment, the nitridation precursor may be LaKNaNbO 5 。LaKNaNbO 5 Having a tetragonal system and comprising LaNaNbO 5 - In which K is + The ions fill the interlayer space. Each of LaNaNbO 5 - NaO in the layer 5 And NbO 5 The pyramid structures are arranged alternately in a "checkerboard" pattern. In the nitriding treatment process, volatile elements contained in the layered oxides volatilize at high temperature, and at the moment, nitrogen atoms replace vacant positions of the volatile elements, the structural morphology of the layered oxides is kept, but the generated nitrogen oxide nanosheets are endowed with rich active sites, and the catalytic activity of the nitrogen oxide nanosheets is improved. Specifically, the generated nitrogen oxide nanosheet is LaNbON 2 In the nitriding process, the volatile metal K, na and other species are selected from LaKNaNbO 5 Volatilizing the surface, and adding the rest La and NbAnd O atom is carried along in an ammonia atmosphere [010]]The direction can be quickly converted into LanbON 2 Meanwhile, the original flaky shape can be kept, and LaNbON is endowed 2 Has an orthorhombic perovskite structure with La atoms arranged in NbO 2 N 4 The upper and lower sides of the octahedron. In addition, la 3+ And Nb 5 + In LaKNaNbO 5 Middle rim [001]Arrangement of atoms in the direction of LaNbON 2 Middle rim [010]The atomic arrangement of the directions substantially coincide.
In step S02, the layered oxide is subjected to a peeling treatment to obtain a single-layer or a small amount of multilayer oxide nanosheets.
In some embodiments, a cation exchange reagent-assisted liquid phase ultrasonic method is used for stripping along the [001] crystal phase direction of the layered oxide to obtain oxide nanosheets with different layers, specifically, the layered oxide is added into an acidic reagent for stirring and centrifugal washing, and then the treated layered oxide is added into an alkaline reagent for liquid phase ultrasonic treatment along the [001] crystal phase direction to obtain oxide nanosheet dispersion with different layers. And performing centrifugal separation treatment on the oxide nanosheet dispersion liquid to obtain the oxide nanosheets with the target layer number, specifically, performing centrifugal separation treatment on the oxide nanosheet dispersion liquid with different layer numbers by using a centrifugal machine according to a set separation rotating speed to obtain the oxide nanosheets with the target layer number.
And carrying out centrifugal separation treatment on the oxide sheets with different layers according to the separation interval by utilizing a separation technology to obtain the oxide sheets with a few layers. And carrying out centrifugal separation treatment on the oxide nanosheet dispersion liquid to obtain the oxide nanosheets with the target layer number. In an embodiment, the number of layers to obtain the target number of layers of oxide nanoplates can be 1-100, the size area of the oxide nanoplates being 100nm 2 -20μm 2 。
Specifically, the cation exchange agent includes at least one of an acid, a base, and an inorganic salt, but is not limited thereto. In particular embodiments, the acid may include, but is not limited to, HCl and H 2 SO 4 The base may include, but is not limited to, at least one of LiOH, naOH, and KOH, and the inorganic salt may beIncluding but not limited to LiCl, naCl, KCl, liNO 3 、NaNO 3 And KNO 3 At least one of (a); the acid may be H 2 SO 4 Alternatively, nitric acid, KOH, and KCl may be used as the base.
Specifically, the separation interval is 1-20000r/min. In a specific implementation, the centrifugal separation interval can be 3000-6000r/min, and can also be 9000-20000r/min. According to the embodiment, the ultrathin oxide film can be obtained by setting the separation interval, the ultrathin flaky shape is convenient for photo-generated charges to rapidly move to the surface, so that the charge separation efficiency is remarkably improved, the activity of hydrogen evolution and oxygen evolution in water decomposition and oxygen evolution of narrow-band nitrogen oxide photocatalysis is improved and optimized, and a new thought is provided for customizing a high-efficiency nitrogen oxide photocatalyst.
In this embodiment, a cation exchange reagent-assisted liquid phase ultrasonic stripping method is used to strip a layered oxide along a [001] crystal phase direction, so as to obtain 1-5 layers of oxide nanosheets along the [001] crystal phase direction, specifically obtain 1 or 2 layers of oxide nanosheets, and further improve the nitridation condition, so that the [001] crystal-oriented oxide sheet can be rapidly converted into a nitrogen oxide nanosheet matched with the oxide sheet in a lattice manner along a [010] crystal phase direction in the nitridation treatment process. Meanwhile, the flaky shape of the ultrathin nitrogen oxide nanosheet is convenient for photo-generated charges to rapidly move to the surface, so that the charge separation efficiency is remarkably improved, and the photocatalytic water decomposition activity of the nitrogen oxide nanosheet is effectively improved.
In step S03, the oxide sheet is subjected to nitridation treatment, so that nitrogen atoms are doped at positions to replace volatile metal elements, thereby obtaining a nitrogen oxide nanosheet.
In an embodiment, the nitridation temperature may range from 600 to 950 ℃ and the nitridation time may range from 0.5 to 20 hours. In a specific implementation, the nitridation time may be 1h, and the nitridation temperature may be 800 ℃. By setting the nitriding time and the nitriding temperature of the nitriding treatment and utilizing the volatilization characteristic of volatile metal elements, nitrogen atoms are doped to replace the positions of the volatile metal elements, so that the oxide nanosheets can quickly convert the oxide sheet in the [001] crystal direction into the nitrogen oxide nanosheets matched with the crystal lattices of the oxide sheet along the [010] crystal phase direction under the mild nitriding condition.
In some embodiments, the few-layer nitroxide nanoplatelets may have a layer number in the range of 1-100 layers, with the nitroxide nanoplatelets having a size area of 100nm 2 -20μm 2 . In a specific implementation, the number of layers may be 1 or 2. The prepared ultrathin oxide nanosheet is realized by adjusting the separation interval range, the ultrathin flaky shape is convenient for photo-generated charges to rapidly move to the surface, so that the charge separation efficiency is remarkably improved, the activity of hydrogen and oxygen evolution in water decomposition of narrow-band nitrogen oxide in photocatalysis is improved and optimized, and a new thought is provided for customizing a high-efficiency nitrogen oxide photocatalyst.
In a second aspect, the present application provides a nitroxide nanosheet. The nitrogen oxide nanosheet is prepared by the preparation method, has broad spectrum capture capability, and can be used for photocatalysts and anti-photocatalytic antibacterial agents.
In a third aspect, an embodiment of the present application further provides a photocatalyst, where a nitrogen oxide nanosheet included in the photocatalyst has a broad-spectrum capture capability, and when the photocatalyst is used in a photocatalytic hydrogen production reaction, the photocatalyst can generate a photo-generated charge in response to visible light, and meanwhile, the surface-modified cocatalyst enhances the charge separation efficiency, and can improve the photocatalytic activity, thereby improving the photocatalytic activity for water decomposition and hydrogen evolution.
Can improve the photocatalytic activity and further improve the activity of hydrogen and oxygen evolution of photocatalytic water decomposition.
In a fourth aspect, embodiments of the present application further provide a photocatalytic antibacterial agent, where the photocatalytic antibacterial agent includes a nitrogen oxide nanosheet, when used for photocatalytic antibacterial, the nitrogen oxide nanosheet responds to visible light under the visible light due to its broad-spectrum capture capability to generate a photo-generated charge, and the co-catalyst modified on the surface effectively activates oxygen molecules to generate bactericidal active species (such as singlet oxygen) to perform an antibacterial and disinfection function under the visible light.
The following description will be given with reference to specific examples.
Example 1
A preparation method of a nitrogen oxide nanosheet (the number of layers is 1-5), comprising the following steps:
S01：
narrow nitrogen oxide nanosheet (with 1-5 layers of LaNbON) 2 Nanosheet) process comprising the steps of:
s01: preparation of layered oxide LaKNaNbO by NaOH/KOH molten salt method 5 And nitriding the precursor.
Taking 5mmol of La 2 O 3 And 5mmol Nb 2 O 5 Placing in a mortar and grinding thoroughly to obtain La 2 O 3 、Nb 2 O 5 Mixing; then La is added 2 O 3 、Nb 2 O 5 Transferring the mixture into an alumina crucible, adding 10g of KOH and 5g of NaOH, putting the alumina crucible into a muffle furnace, heating to 873K at the heating rate of 10K/min, preserving heat at the temperature of 873K for 3 hours, cooling to 773K, preserving heat at the temperature of 773K for 15 hours, and naturally cooling to room temperature to obtain LaKNaNbO 5 A reaction product; finally washing the reaction product for 3-5 times by using ultrapure water at room temperature, centrifuging to remove residual NaOH and KOH, and then drying in vacuum to obtain the layered oxide LaKNaNbO 5 。
S02: liquid phase ultrasonic method assisted by dilute nitric acid [001]]Stripping in the crystal phase direction to obtain LaKNaNbO with different layers 5 The nanosheet dispersion is centrifuged to obtain LaKNaNbO with different layers according to a centrifugal interval of 9000-20000r/min 5 Centrifugal separation treatment is carried out on the nano-sheet dispersion liquid to obtain LaKNaNbO with target layer number 5 Nanosheets.
The method specifically comprises the following steps: 2g of LaKNaNbO is taken 5 Adding the nanosheet powder into 50mL (1 mol/L) of nitric acid, stirring for 2 hours, and centrifuging and washing for 3-5 times to remove redundant dilute nitric acid; then the treated LaKNaNbO 5 The nanosheet sample is placed in a saturated KOH solution for ultrasonic stripping for 2-5 hours to obtain LaKNaNbO with different layer numbers 5 A nanosheet dispersion.
Setting the separation interval at 9000-20000r/min, and centrifuging to obtain LaKNaNbO with different layers according to the separation interval 5 Centrifugal separation of nanosheet dispersionProcessing to obtain LaKNaNbO with the target layer number of 1-5 5 A nanosheet.
S03: for LaKNaNbO with 1-5 layers 5 The nano-sheet is subjected to nitriding treatment to obtain a crystal phase of [001]]LaKNaNbO of 5 Nanosheet along crystal phase [010]]Fast conversion to Lanbon 2 A nanosheet.
Taking LaKNaNbO with 1-5 layers 5 The nano-sheets are put into a tube furnace and are nitrided at the temperature of 600 ℃ for 0.5 hour to obtain LaNbON 2 Nanosheets. The specific chemical reaction equation is as follows:
3LaKNaNbO 5 +8NH 3 ＝3LaNbON 2 +3Na (volatile) +3K (volatile) +12H 2 O+N 2
Example 2
Narrow nitrogen oxide nanosheet (5-50 layers of LaNbON) 2 Nanoplatelets) comprising the steps of:
s01: preparation of layered oxide LaKNaNbO by NaOH/KOH molten salt method 5 And nitriding the precursor.
5mmol of La was taken 2 O 3 And 5mmol Nb 2 O 5 Placing in a mortar and grinding thoroughly to obtain La 2 O 3 、Nb 2 O 5 Mixing; then La is added 2 O 3 、Nb 2 O 5 Transferring the mixture into an alumina crucible, adding 10g of KOH and 5g of NaOH, putting the alumina crucible into a muffle furnace, heating to 873K at a heating rate of 10K/min, preserving heat at 873K for 3 hours, cooling to 773K, preserving heat at 773K for 15 hours, and naturally cooling to room temperature to obtain LaKNaNbO 5 A reaction product; finally washing the reaction product for 3-5 times by using ultrapure water at room temperature, centrifuging to remove residual NaOH and KOH, and then drying in vacuum to obtain the layered oxide LaKNaNbO 5 。
S02: liquid phase ultrasonic method assisted by dilute nitric acid [001]]Stripping in the crystal phase direction to obtain LaKNaNbO with different layers 5 The nanosheet dispersion is centrifuged by a centrifuge at 6000-9000r/min to obtain LaKNaNbO with different layers 5 Centrifugal separation treatment is carried out on the nano-sheet dispersion liquid to obtain the targetLayer number of LaKNaNbO 5 A nanosheet.
The method specifically comprises the following steps: 2g of LaKNaNbO is taken 5 Adding the nanosheet powder into 50mL (1 mol/L) of nitric acid, stirring for 2 hours, and centrifuging and washing for 3-5 times to remove redundant dilute nitric acid; then the treated LaKNaNbO 5 The nanosheet sample is placed in a saturated KOH solution for ultrasonic stripping for 2-5 hours to obtain LaKNaNbO with different layers 5 A nanosheet dispersion.
Setting the separation interval at 6000-9000r/min, and centrifuging to obtain LaKNaNbO with different layers according to the separation interval 5 Centrifugal separation treatment is carried out on the nano-sheet dispersion liquid to obtain LaKNaNbO with 5-50 target layers 5 Nanosheets.
S03: for LaKNaNbO with 5-50 layers 5 The nano-sheet is subjected to nitriding treatment to obtain a crystal phase of [001]]LaKNaNbO of 5 Nanosheet along crystal phase [010]]Fast conversion to LanbON 2 Nanosheets.
Taking LaKNaNbO with 5-50 layers 5 The nano-sheets are put into a tube furnace and are nitrided at the temperature of 600 ℃ for 0.5 hour to obtain LaNbON 2 Nanosheets. The specific chemical reaction equation is as follows:
3LaKNaNbO 5 +8NH 3 ＝3LaNbON 2 +3Na (volatile) +3K (volatile) +12H 2 O+N 2
Example 3
Nitrogen oxide nanosheet (with 50-200 layers of LaNbON) 2 Nanoplatelets) comprising the steps of:
narrow nitrogen oxide nanosheet (LaNbON with number of layers of 50-200) 2 Nanoplatelets) comprising the steps of:
s01: preparation of layered oxide LaKNaNbO by NaOH/KOH molten salt method 5 And nitriding the precursor.
5mmol of La was taken 2 O 3 And 5mmol Nb 2 O 5 Placing in a mortar and grinding thoroughly to obtain La 2 O 3 、Nb 2 O 5 Mixing; then La 2 O 3 、Nb 2 O 5 The mixture was transferred to an alumina crucible and added 10g KOH and 5g NaOH, then putting an alumina crucible into a muffle furnace, heating to 873K at the heating rate of 10K/min, preserving the heat at 873K for 3 hours, then cooling to 773K, preserving the heat at 773K for 15 hours, and naturally cooling to room temperature to obtain LaKNaNbO 5 A reaction product; finally washing the reaction product for 3-5 times by using ultrapure water at room temperature, centrifuging to remove residual NaOH and KOH, and then drying in vacuum to obtain the layered oxide LaKNaNbO 5 。
S02: liquid phase ultrasonic method assisted by dilute nitric acid [001]]Stripping in the crystal phase direction to obtain LaKNaNbO with different layers 5 The nanosheet dispersion is centrifuged by a centrifuge at 3000-6000r/min to obtain LaKNaNbO with different layers 5 Centrifugal separation treatment is carried out on the nano-sheet dispersion liquid to obtain LaKNaNbO with the target layer number 5 Nanosheets.
The method comprises the following specific steps: 2g of LaKNaNbO is taken 5 Adding the nanosheet powder into 50mL (1 mol/L) of nitric acid, stirring for 2 hours, and centrifuging and washing for 3-5 times to remove redundant dilute nitric acid; then the treated LaKNaNbO 5 The nanosheet sample is placed in a saturated KOH solution for ultrasonic stripping for 2-5 hours to obtain LaKNaNbO with different layers 5 A nanosheet dispersion.
Setting the separation interval at 3000-6000r/min, and centrifuging to remove LaKNaNbO with different layers according to the separation interval 5 Centrifugal separation treatment is carried out on the nano-sheet dispersion liquid to obtain LaKNaNbO with 50-200 target layers 5 A nanosheet.
S03: for LaKNaNbO with 50-200 layers 5 The nano-sheet is subjected to nitriding treatment to obtain a crystal phase of [001]]LaKNaNbO (LaKNaNbO) 5 Nanosheet along crystal phase [010]]Fast conversion to Lanbon 2 Nanosheets.
Taking LaKNaNbO with 50-200 layers 5 The nano-sheets are put into a tube furnace and are nitrided at the temperature of 600 ℃ for 0.5 hour to obtain LaNbON 2 Nanosheets. The specific chemical reaction equation is as follows:
3LaKNaNbO 5 +8NH 3 ＝3LaNbON 2 +3Na (volatile) +3K (volatile) +12H 2 O+N 2
Example 4
Nitrogen oxide nanosheet (200-800 layers of LaNbON) 2 Nanosheet) process comprising the steps of:
s01: preparation of layered oxide LaKNaNbO by NaOH/KOH molten salt method 5 And nitriding the precursor.
Taking 5mmol of La 2 O 3 And 5mmol Nb 2 O 5 Placing in a mortar and sufficiently grinding to obtain La 2 O 3 、Nb 2 O 5 Mixing; then La is added 2 O 3 、Nb 2 O 5 Transferring the mixture into an alumina crucible, adding 10g of KOH and 5g of NaOH, putting the alumina crucible into a muffle furnace, heating to 873K at the heating rate of 10K/min, preserving heat at the temperature of 873K for 3 hours, cooling to 773K, preserving heat at the temperature of 773K for 15 hours, and naturally cooling to room temperature to obtain LaKNaNbO 5 A reaction product; finally washing the reaction product for 3-5 times by using ultrapure water at room temperature, centrifuging to remove residual NaOH and KOH, and then drying in vacuum to obtain the layered oxide LaKNaNbO 5 。
S02: liquid phase ultrasonic method assisted by dilute nitric acid [001]]Stripping in the crystal phase direction to obtain LaKNaNbO with different layers 5 The nanosheet dispersion is subjected to different layer numbers of LaKNaNbO by using a centrifugal machine according to the centrifugal interval of 1000-3000r/min 5 Centrifugal separation treatment is carried out on the nano-sheet dispersion liquid to obtain LaKNaNbO with the target layer number 5 Nanosheets.
The method specifically comprises the following steps: 2g of LaKNaNbO is taken 5 Adding the nanosheet powder into 50mL (1 mol/L) of nitric acid, stirring for 2 hours, and centrifuging and washing for 3-5 times to remove redundant dilute nitric acid; then the treated LaKNaNbO 5 The nanosheet sample is placed in a saturated KOH solution for ultrasonic stripping for 2-5 hours to obtain LaKNaNbO with different layers 5 A nanosheet dispersion.
Setting the separation interval to 1000-3000r/min, and centrifuging to obtain LaKNaNbO with different layers according to the separation interval 5 Centrifugal separation treatment is carried out on the nano-sheet dispersion liquid to obtain LaKNaNbO with 50-200 target layers 5 Nanosheets.
S03: for LaKNaNbO with 200-800 layers 5 The nano-sheet is subjected to nitriding treatment to obtain a crystal phase of [001]]LaKNaNbO of 5 Nanosheet along crystal phase [010]]Fast conversion to LanbON 2 Nanosheets.
Taking LaKNaNbO with 200-800 layers 5 The nano-sheets are put into a tube furnace and are nitrided at the temperature of 600 ℃ for 0.5 hour to obtain LaNbON 2 Nanosheets. The specific chemical reaction equation is as follows:
3LaKNaNbO 5 +8NH 3 ＝3LaNbON 2 +3Na (volatile) +3K (volatile) +12H 2 O+N 2
Comparative example
A preparation method of nitrogen oxide comprises the following steps:
s01: preparation of layered oxide LaKNaNbO by NaOH/KOH molten salt method 5 As a nitridation precursor.
5mmol of La was taken 2 O 3 And 5mmol Nb 2 O 5 Placing in a mortar and sufficiently grinding to obtain La 2 O 3 、Nb 2 O 5 Mixing; then La 2 O 3 、Nb 2 O 5 Transferring the mixture into an alumina crucible, adding 10g of KOH and 5g of NaOH, putting the alumina crucible into a muffle furnace, heating to 873K at the heating rate of 10K/min, preserving heat at the temperature of 873K for 3 hours, cooling to 773K, preserving heat at the temperature of 773K for 15 hours, and naturally cooling to room temperature to obtain LaKNaNbO 5 A reaction product; finally washing the reaction product for 3-5 times by using ultrapure water at room temperature, centrifuging to remove residual NaOH and KOH, and then drying in vacuum to obtain the layered oxide LaKNaNbO 5 。
S02: the layered oxide LaKNaNbO 5 Putting the mixture into a tube furnace, and performing nitriding treatment for 0.5 hour at the temperature of 600 ℃ to obtain LaNbON 2 。
Photocatalytic activity experimental comparative analysis:
TABLE 1
The comparative analysis of the photocatalytic activity test results in table 1 above leads to the following conclusions:
the passing-through LaKNaNbO provided by the embodiments 1 to 4 of the application is adopted 5 The nano-sheet dispersion liquid is centrifugally separated in different separation intervals to obtain LaKNaNbO with corresponding target layer number 5 Nanosheets, thereby setting different numbers of layers of Lanbonbon 2 Photocatalytic activity, as can be seen from the results of the experiment: lanbON 2 The fewer the number of nanosheet layers, i.e. LanbON 2 The thinner the nanosheet is, the higher the hydrogen evolution activity and the oxygen evolution activity are; while the comparative example has no layered oxide LaKNaNbO 5 Stripping to directly remove LaKNaNbO 5 Nitriding to obtain LaNbON 2 Relative to the Lanbon obtained by the stripping treatment 2 Nanosheets, laNbON 2 The hydrogen evolution activity and oxygen evolution activity are both minimal, further illustrating the application by following [001]]Crystalline phase orientation opposite layered oxide LaKNaNbO 5 And stripping treatment is carried out to obtain an ultrathin flaky shape, so that photo-generated charges can be conveniently and rapidly moved to the surface, the charge separation efficiency is enhanced, and the photocatalytic activity is improved, namely the nitrogen oxide nanosheet can enhance the photocatalytic water decomposition activity.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. A preparation method of a nitrogen oxide nanosheet is characterized by comprising the following steps:
mixing each source compound of the oxide with a fluxing agent in an oxygen environment, then carrying out melting treatment, cooling, and then carrying out purification treatment to obtain the layered oxide;
stripping the layered oxide along the [001] crystal phase direction of the layered oxide by using a cation exchange reagent-assisted liquid phase ultrasonic method to obtain oxide nanosheets with different layers, specifically, adding the layered oxide into an acidic reagent to perform stirring and centrifugal washing treatment, and then adding the treated layered oxide into an alkaline reagent to perform liquid phase ultrasonic treatment along the [001] crystal phase direction to obtain oxide nanosheet dispersion liquid with different layers; performing centrifugal separation treatment on the oxide nanosheet dispersion liquid to obtain the oxide nanosheets with the target layer number, specifically, performing centrifugal separation treatment on the oxide nanosheet dispersion liquid with different layer numbers by using a centrifugal machine according to a set separation rotating speed to obtain the oxide nanosheets with the target layer number;
nitriding the oxide nanosheet to obtain a nitrogen oxide nanosheet;
wherein the temperature of the nitriding treatment is 600-950 ℃, and the time is 0.5-20h;
the fluxing agent contains volatile metal elements including sodium chloride, potassium chloride, lithium chloride, cesium chloride, magnesium chloride, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, magnesium hydroxide and Na 2 CO 3 At least one of;
the layered oxide comprises LaKNaTaO 5 、LaKNaNbO 5 、(Na 1/4 Ba 3/4 )(Zn 1/4 Ta 3/4 )O 3 、KLaTa 2 O 7 And KCa 2 Nb 3 O 10 At least one of (1).
2. The method for preparing an oxynitride nanosheet according to claim 1, wherein the method of nitriding the oxide plate to obtain an oxynitride nanosheet comprises the steps of:
and nitriding the oxide sheet to dope a nitrogen atom to replace a volatile metal element position, so as to obtain the nitrogen oxide nanosheet.
3. The method of producing a nitroxide nanoplatelet of any of claims 1-2, wherein the number of layers of nitroxide nanoplatelet is 1-100 layers; and/or
The area size of the nitrogen oxide nanosheet is 100nm 2 -20μm 2 。
4. A method of preparing a nitroxide nanoplate as claimed in any of claims 1-2,
the volatile metal element is present in the layered oxide in the form of ions.
5. An oxynitride nanoplatelet comprising the oxynitride nanoplatelet of any of claims 1-4.
6. A photocatalyst, characterized in that it comprises the nitrogen oxide nanoplatelets of claim 5.
7. A photocatalytic antimicrobial agent, characterized by comprising the nitrogen oxide nanoplatelets of claim 5.
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| JP2017128458A (en) * | 2016-01-18 | 2017-07-27 | 富士フイルム株式会社 | Oxynitride fine particle, photocatalyst for water decomposition, photocatalyst electrode for generating hydrogen and oxygen, photocatalyst module for generating hydrogen and oxygen and manufacturing method of oxynitride fine particle |
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