CN111905796A - Preparation method of superfine metal nanoparticle/carbon nitride nanosheet composite material - Google Patents
Preparation method of superfine metal nanoparticle/carbon nitride nanosheet composite material Download PDFInfo
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- CN111905796A CN111905796A CN202010909441.9A CN202010909441A CN111905796A CN 111905796 A CN111905796 A CN 111905796A CN 202010909441 A CN202010909441 A CN 202010909441A CN 111905796 A CN111905796 A CN 111905796A
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002135 nanosheet Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004202 carbamide Substances 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003892 spreading Methods 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 238000012719 thermal polymerization Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 10
- 239000002923 metal particle Substances 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- B01J35/39—
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/23—
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- B01J35/393—
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- B01J35/40—
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
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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
- 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
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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
- 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
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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
- 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
- C01B2203/1058—Nickel catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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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 invention discloses a preparation method of an ultrafine metal nanoparticle/carbon nitride nanosheet composite material, and belongs to the technical field of material preparation and photocatalysis. During preparation, melamine or urea is used as a precursor, bulk-phase carbon nitride is prepared through thermal polymerization, and the prepared bulk-phase carbon nitride is prepared into carbon nitride nanosheets through a thermal stripping method in an air muffle furnace; mixing metal salt and carbon nitride nanosheets according to a certain mass ratio, adding a proper amount of solid sodium borohydride, fully grinding, washing and drying to obtain the superfine metal nanoparticle/carbon nitride nanosheet composite material. The invention utilizes the principle of solid-phase reduction reaction, the raw materials are cheap and easy to obtain, the process flow is simple and environment-friendly, and the obtained composite material has excellent visible light catalytic performance and can be widely applied to the field of photocatalysis.
Description
Technical Field
The invention relates to the technical field of material preparation and photocatalysis, in particular to a preparation method of a superfine metal nanoparticle/carbon nitride nanosheet composite material.
Background
Carbon nitride is used as a novel organic polymer semiconductor photocatalytic material and is widely applied to the technical field of photocatalysis, for example, the carbon nitride can be used for preparing organic fuels by photocatalytic organic synthesis and photocatalytic reduction of carbon dioxide, photocatalytic degradation of organic pollutants, photocatalytic decomposition of aquatic hydrogen and the like, and in addition, the carbon nitride material has good application value in the fields of environmental protection, energy, chemical industry and the like.
The common carbon nitride material has good chemical stability, low preparation cost and environmental friendliness, but the photon-generated carrier has high recombination probability and small specific surface area, so that the application of the material in the field of photocatalysis is limited. In order to improve the photocatalytic performance of carbon nitride, the mainstream method is to improve the specific surface area of carbon nitride by surface morphology control and to inhibit the recombination of photo-generated electrons and holes by loading metal particles or other semiconductor particles. Therefore, the metal nano-particle/carbon nitride composite material becomes a photocatalytic material with more application value.
For the metal nanoparticle/carbon nitride composite material, theory and practice prove that the smaller the particle size of the metal particles in the composite material, the higher the dispersibility, the better the photocatalytic performance of the composite material, because the metal particles have higher specific surface area and larger contact area with the carbon nitride, which is beneficial to conducting and capturing photogenerated electrons and holes in the carbon nitride.
In order to prepare the ultrafine metal nanoparticle/carbon nitride composite material with high dispersibility, the traditional preparation method is mainly a liquid phase deposition method, namely, carbon nitride and metal salt are dispersed in a solution, and then a reducing agent is added to reduce the metal salt into metal particles. In order to reduce the metal particle size and prevent the metal particles from aggregating, the method needs to add a large amount of organic reagent as a polymerization inhibitor in the reaction, and the obtained material needs to wash away the organic reagent by using a large amount of washing liquid, so that the preparation cost is increased, a large amount of organic waste liquid is generated, the economy is low, and the environmental protection is not facilitated.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a novel preparation method of a superfine metal nanoparticle/carbon nitride nanosheet composite material, wherein a solid phase grinding method is used for the first time, the reaction process is simple and easy to implement, raw materials are easy to obtain, the cost is low, an organic reagent is not required in the process flow, the environment is protected, the particle size of metal nanoparticles in the prepared material is only 1-5 nm, the metal particles are high in dispersity, and the composite material is excellent in photocatalytic performance.
The technical scheme of the invention is as follows:
a preparation method of an ultrafine metal nanoparticle/carbon nitride nanosheet composite material comprises the following specific preparation steps:
(1) placing melamine or urea in a crucible, and reacting in an air muffle furnace to obtain a carbon nitride material;
(2) grinding the carbon nitride prepared in the step (1), uniformly spreading the obtained carbon nitride powder in a quartz boat, and reacting in an air muffle furnace to prepare carbon nitride nanosheets;
(3) mixing the metal salt solid with the carbon nitride nanosheet obtained in the step (2) according to a certain mass ratio, adding a certain mass of sodium borohydride solid, and fully grinding in a mortar for a period of time to obtain a powder sample;
(4) and (3) washing the powder sample obtained in the step (3) with pure water, centrifuging, removing the upper layer solution, repeating the washing and centrifuging processes for 6-10 times, and drying the solid in a vacuum drying oven to obtain the superfine metal nanoparticle/carbon nitride nanosheet composite material.
Furthermore, the particle size of the metal nanoparticles on the obtained superfine metal nanoparticle/carbon nitride nanosheet composite material is 1-5 nm.
Further, in the step (1), the reaction condition in the air muffle furnace is that the reaction is finished by heating to 550 ℃ at the speed of 4.4 ℃/min and then preserving the temperature for 4 hours.
Further, in the step (2), the reaction condition in the air muffle furnace is that the temperature is increased to 500 ℃ at the speed of 5-10 ℃/min, and then the temperature is maintained for 1-2 hours to complete the reaction.
Further, in the step (4), the centrifugal rotating speed is 3000 r/min, and the drying condition of the vacuum drying oven is vacuum drying for 12-24 hours at the temperature of 60-80 ℃.
Further, in the step (3), the metal salt solid includes cobalt chloride, cobalt nitrate, nickel chloride, nickel nitrate, zinc chloride, zinc nitrate, manganese chloride, manganese nitrate, copper chloride, and copper nitrate.
Further, in the step (3), the mass ratio of the metal salt solid to the carbon nitride nanosheet is 1: 50-1: 1.
Further, in the step (3), the mass ratio of the sodium borohydride to the metal salt solid is 1: 1-3: 1.
Further, the grinding time in the step (3) is 30 min to 100 min.
The invention has the beneficial effects that:
1. the metal nanoparticle/carbon nitride nanosheet composite material is prepared by a solid phase grinding method for the first time, the whole process is simple and easy to implement, raw materials are easy to obtain, and the cost is low;
2. organic reagents are not needed in the preparation process flow, and compared with the common preparation process in the prior art, the preparation process does not generate a large amount of organic waste liquid and is environment-friendly;
3. the composite material prepared by the method disclosed by the invention has the advantages that the particle size of the metal nanoparticles is superfine and is only 1-5 nm, the metal particles have high dispersibility, the photo-generated electrons and holes in the carbon nitride can be conducted and captured, the photocatalytic performance is excellent, and the composite material can be applied to the fields of hydrogen preparation by photocatalytic water decomposition, photocatalytic organic pollutant degradation, photocatalytic organic synthesis and the like.
Drawings
FIG. 1 is a transmission electron microscope photograph of the ultra-fine metal nanoparticle/carbon nitride nanosheet composite obtained in example 1;
FIG. 2 is an X-ray diffraction pattern of the ultra-fine metallic nanoparticle/carbon nitride nanosheet composite obtained in example 1;
fig. 3 is a graph comparing the photocatalytic water splitting hydrogen production performance of the ultra-fine metal nanoparticle/carbon nitride nanosheet composite material obtained in example 1 and common carbon nitride.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1
1. Taking 20 g of melamine, placing the melamine in a crucible, covering the crucible, placing the crucible in a muffle furnace, heating the melamine to 550 ℃ at the speed of 4.4 ℃/min, keeping the temperature for 4 hours, and naturally cooling the melamine to room temperature to obtain carbon nitride;
2. grinding the fired carbon nitride, then uniformly spreading a proper amount of the carbon nitride on a quartz boat in batches, putting the quartz boat in a muffle furnace, heating to 500 ℃ at the speed of 5.6 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature to obtain carbon nitride nanosheets;
3. weighing 0.20 g of the carbon nitride nanosheet obtained in the step 2 and 0.010 g of CoCl by using an electronic balance2Mixing and grinding in a mortar for 15 min; then 0.010 g NaBH is weighed4Adding the solid into a mortar, and grinding for 30 min;
4. and after grinding, placing the product obtained by grinding in a centrifuge tube, adding a proper amount of water, performing ultrasonic washing for 5 min, centrifuging at the rotating speed of 3000 r/min, removing the upper-layer solution, repeating the washing and centrifuging processes for 6 times, placing the solid in a vacuum drying oven, and performing vacuum drying at 60 ℃ for 12 hours to obtain the superfine cobalt nanoparticle/carbon nitride nanosheet composite material.
The transmission electron microscopy image of the obtained composite material is shown in fig. 1, and it can be known from the image that in the composite material prepared by the method, the particle size of the metal cobalt nanoparticles is 1-4 nm, the metal cobalt nanoparticles are highly dispersed and uniformly distributed on the surface of the carbon nitride nanosheet. Wherein d is an electron diffraction pattern of a transmission electron microscope, and d =0.2048 nm is a lattice spacing measured from the lattice in the picture, which is identical to the theoretical lattice spacing of metallic cobalt, so that it can be proved that the crystals on the carbon nitride nanosheets are metallic cobalt nanoparticles.
The X-ray diffraction (XRD) of the resulting composite material is shown in fig. 2: in an XRD characterization diagram, a 27.8-degree diffraction peak in the cobalt/carbon nitride composite material is an 002-face characteristic diffraction peak of carbon nitride, obvious diffraction peaks appear at 55-degree and 41-degree positions of larger cobalt metal particles, and the two diffraction peaks do not appear in the diagram, which further indicates that in the composite material prepared by the preparation method, the metal nanoparticles have small particle size and high dispersity.
The result of hydrogen production by photocatalytic decomposition of the obtained composite material is shown in fig. 3: the photocatalytic hydrogen production performance of the superfine cobalt nanoparticle/carbon nitride nanosheet composite material prepared by the embodiment is higher than that of common carbon nitride, and is about 10 times of the hydrogen production rate.
Example 2
1. Taking 20 g of melamine, placing the melamine in a crucible, covering the crucible, placing the crucible in a muffle furnace, heating the melamine to 550 ℃ at the speed of 4.4 ℃/min, keeping the temperature for 4 hours, and naturally cooling the melamine to room temperature to obtain carbon nitride;
2. grinding the fired carbon nitride, then uniformly spreading a proper amount of the carbon nitride on a quartz boat in batches, putting the quartz boat in a muffle furnace, heating to 500 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 h, and cooling to room temperature to obtain carbon nitride nanosheets;
3. weighing 0.20 g of carbon nitride nanosheet and 0.050 g of nickel chloride in an electronic balance, and mixing and grinding for 20 min; then 0.100 g of NaBH was weighed4Adding the solid into a mortar, and grinding for 60 min; and after grinding, placing the product obtained by grinding in a centrifuge tube, adding a proper amount of water, performing ultrasonic washing for 5 min, centrifuging at the rotating speed of 3000 r/min, removing the upper-layer solution, repeating the washing and centrifuging processes for 8 times, placing the solid in a vacuum drying oven, and performing vacuum drying at 60 ℃ for 24 hours to obtain the superfine nickel nanoparticle/carbon nitride nanosheet composite material.
In the composite material prepared by the method, the particle size of the metallic nickel nano particles is 2-5 nm, the dispersibility is high, and the metallic nickel nano particles are uniformly distributed on the carbon nitride nano sheet. The material is used for photocatalytic degradation of rhodamine B, and the catalytic degradation rate of the material is about 6 times that of common carbon nitride.
Example 3
1. Taking 20 g of melamine, placing the melamine in a crucible, covering the crucible, placing the crucible in a muffle furnace, heating the melamine to 550 ℃ at the speed of 4.4 ℃/min, keeping the temperature for 4 hours, and naturally cooling the melamine to room temperature to obtain carbon nitride;
2. grinding the fired carbon nitride, then uniformly spreading a proper amount of the carbon nitride on a quartz boat in batches, putting the quartz boat in a muffle furnace, heating to 500 ℃ at the speed of 8 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature to obtain carbon nitride nanosheets;
3. weighing 0.20 g of carbon nitride nanosheet and 0.150 g of manganese chloride in an electronic balance, mixing and grinding for 30 min; then 0.200 g NaBH was weighed4Adding the solid into a mortar, and grinding for 50 min; and after grinding, placing the ground product in a centrifuge tube, adding a proper amount of water, performing ultrasonic washing for 5 min, centrifuging at the rotating speed of 3000 r/min, removing the upper-layer solution, repeating the washing and centrifuging processes for 8 times, placing the solid in a vacuum drying oven, and performing vacuum drying at 80 ℃ for 12 hours to obtain the superfine manganese nanoparticle/carbon nitride nanosheet composite material.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (9)
1. A preparation method of an ultrafine metal nanoparticle/carbon nitride nanosheet composite material is characterized by comprising the following specific preparation steps:
(1) placing melamine or urea in a crucible, and reacting in an air muffle furnace to obtain a carbon nitride material;
(2) grinding the carbon nitride prepared in the step (1), uniformly spreading the obtained carbon nitride powder in a quartz boat, and reacting in an air muffle furnace to prepare carbon nitride nanosheets;
(3) mixing the metal salt solid with the carbon nitride nanosheet obtained in the step (2) according to a certain mass ratio, adding a certain mass of sodium borohydride solid, and grinding in a mortar to obtain a powder sample;
(4) and (3) washing the powder sample obtained in the step (3) with pure water, centrifuging, removing the upper layer solution, repeating the washing and centrifuging processes for 6-10 times, and drying the solid in a vacuum drying oven to obtain the superfine metal nanoparticle/carbon nitride nanosheet composite material.
2. The method for preparing the ultrafine metal nanoparticle/carbon nitride nanosheet composite material of claim 1, wherein the metal nanoparticle on the ultrafine metal nanoparticle/carbon nitride nanosheet composite material has a particle size of 1-5 nm.
3. The method for preparing the ultrafine metal nanoparticle/carbon nitride nanosheet composite material of claim 1, wherein in step (1), the reaction is completed by heating to 550 ℃ at a rate of 4.4 ℃/min under the reaction conditions in an air muffle furnace, and then maintaining the temperature for 4 hours.
4. The method for preparing the ultrafine metal nanoparticle/carbon nitride nanosheet composite material according to claim 1, wherein in step (2), the reaction conditions in the air muffle furnace are that the temperature is raised to 500 ℃ at a rate of 5-10 ℃/min, and then the temperature is maintained for 1-2 hours to complete the reaction.
5. The method for preparing the ultrafine metal nanoparticle/carbon nitride nanosheet composite material according to claim 1, wherein in step (4), the centrifugal rotation speed is 3000 r/min, and the drying condition of the vacuum drying oven is vacuum drying at 60-80 ℃ for 12-24 hours.
6. The method for preparing the ultrafine metal nanoparticle/carbon nitride nanosheet composite material of claim 1, wherein in step (3), the metal salt solid comprises cobalt chloride, cobalt nitrate, nickel chloride, nickel nitrate, zinc chloride, zinc nitrate, manganese chloride, manganese nitrate, copper chloride, copper nitrate.
7. The method for preparing the ultrafine metal nanoparticle/carbon nitride nanosheet composite material of claim 1, wherein in step (3), the mass ratio of the metal salt solid to the carbon nitride nanosheet is 1: 50-1: 1.
8. The method for preparing the ultrafine metal nanoparticle/carbon nitride nanosheet composite material of claim 1, wherein in step (3), the mass ratio of sodium borohydride to the metal salt solid is 1: 1-3: 1.
9. The method for preparing the ultrafine metal nanoparticle/carbon nitride nanosheet composite material of claim 1, wherein the milling time in step (3) is 30 min to 100 min.
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