CN110479319B - Au/CuSe tangential heterogeneous nano material and preparation method thereof - Google Patents
Au/CuSe tangential heterogeneous nano material and preparation method thereof Download PDFInfo
- Publication number
- CN110479319B CN110479319B CN201910747931.0A CN201910747931A CN110479319B CN 110479319 B CN110479319 B CN 110479319B CN 201910747931 A CN201910747931 A CN 201910747931A CN 110479319 B CN110479319 B CN 110479319B
- Authority
- CN
- China
- Prior art keywords
- solution
- tangential
- cuse
- heterogeneous
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 106
- 239000010931 gold Substances 0.000 claims abstract description 78
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 40
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910052737 gold Inorganic materials 0.000 claims abstract description 23
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 20
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 20
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 20
- 239000002077 nanosphere Substances 0.000 claims abstract description 19
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- RBRLCUAPGJEAOP-UHFFFAOYSA-M sodium selanide Chemical compound [Na+].[SeH-] RBRLCUAPGJEAOP-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 9
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- ZBKIUFWVEIBQRT-UHFFFAOYSA-N gold(1+) Chemical compound [Au+] ZBKIUFWVEIBQRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 230000012010 growth Effects 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 239000004094 surface-active agent Substances 0.000 claims abstract description 3
- 239000012265 solid product Substances 0.000 claims description 21
- 239000012279 sodium borohydride Substances 0.000 claims description 20
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- -1 sodium selenide hydride Chemical compound 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 239000002107 nanodisc Substances 0.000 abstract description 3
- 230000001808 coupling effect Effects 0.000 abstract description 2
- 239000011807 nanoball Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- NLZOGIZKBBJWPB-UHFFFAOYSA-N [Na].[SeH2] Chemical compound [Na].[SeH2] NLZOGIZKBBJWPB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000035040 seed growth Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a preparation method of an Au/CuSe tangential heterogeneous nano material, which comprises the following steps: s1, preparing a nano gold colloidal solution in a hexadecyl trimethyl ammonium bromide system, wherein the particle size of a gold nano ball is 18-22 nm; s2, preparing a sodium hydroselenide solution, adopting a water-phase synthesis method to take gold nanospheres as a growth substrate, sodium hydroselenide and copper acetate as precursors, ascorbic acid as a reducing agent and hexadecyl trimethyl ammonium bromide as a surfactant, and growing a two-dimensional copper selenide nano disc in the tangential direction of the gold nanospheres by vacuum reaction in the presence of hexamethylenetetramine to obtain an Au/CuSe tangential heterogeneous nanomaterial aqueous solution; and S3, separating, cleaning and drying to obtain the Au/CuSe tangential heterogeneous nano material. The Au/CuSe tangential heterogeneous nano material is prepared by using an all-water phase method, and the obtained heterogeneous nano material has a stable shape structure, an obvious double-plasmon coupling effect and excellent performance of photocatalytic hydrogen generation.
Description
Technical Field
The invention relates to the technical field of inorganic nano material preparation, in particular to an Au/CuSe tangential heterogeneous nano material and a preparation method thereof.
Background
The two-dimensional copper selenide nano disc has the characteristics of excellent photoelectric conversion characteristic, large specific surface area, abundant reaction sites, strong near infrared plasmon photon absorption and the like, and shows great application potential in the field of photocatalysis. However, the two-dimensional copper selenide nanometer material has weak absorption in a visible light wave band and high recombination speed of carriers generated by light excitation, so that the actual photocatalytic performance of the two-dimensional copper selenide nanometer material is greatly limited. The metal nano crystal with the plasmon characteristic is compounded with the two-dimensional semiconductor nano material, and the photocatalysis performance of the heterostructure can be greatly improved under the synergistic effect of the plasmon and the exciton. Since the plasmon optical properties of metal nanocrystals are highly correlated with their morphology and structure, the photocatalytic performance of metal/two-dimensional semiconductor heterogeneous nanomaterials depends largely on their morphology framework. The traditional methods for preparing metal/two-dimensional semiconductor material heterostructures are mainly divided into the following two categories: 1) depositing the metal nano-crystals on the surface of the prepared two-dimensional semiconductor material by a chemical or physical method; 2) and directly mixing the prepared metal nano-crystal and the semiconductor two-dimensional material. The morphology and the structure of the heterostructure prepared by the two methods are difficult to regulate and control, and the utilization rate of plasmon energy is low, so that the photocatalytic performance of the heterostructure is poor.
Disclosure of Invention
The invention provides an Au/CuSe tangential heterogeneous nano material with high-efficiency photocatalytic performance and a preparation method thereof for solving the technical problems.
The technical scheme for solving the technical problems is as follows: a preparation method of Au/CuSe tangential heterogeneous nano material comprises the following steps:
s1, preparing a nano gold colloidal solution in a hexadecyl trimethyl ammonium bromide system, wherein the particle size of gold nanospheres is 18-22 nm;
s2, preparing a sodium hydroselenide solution, taking the gold nanospheres as a growth substrate, taking sodium hydroselenide and copper acetate as precursors, taking ascorbic acid as a reducing agent, taking hexadecyl trimethyl ammonium bromide as a surfactant, and reacting in vacuum in the presence of hexamethylenetetramine to grow a two-dimensional copper selenide nanodisk in the tangential direction of the gold nanospheres to obtain an Au/CuSe tangential heterogeneous nanomaterial aqueous solution, wherein the concentrations of the gold nanospheres, the sodium hydroselenide, the copper acetate, the ascorbic acid, the hexamethylenetetramine and the hexadecyl trimethyl ammonium bromide in a reaction system are respectively 25.96-31.76 nM, 0.52-0.87 mM, 0.48-0.90 mM, 8.08-15.01 mM and 19.63-26.56 mM, the reaction temperature is 85-95 ℃, and the reaction time is 7.5-8.5 h;
and S3, separating, cleaning and drying the Au/CuSe tangential heterogeneous nano material aqueous solution to obtain the Au/CuSe tangential heterogeneous nano material.
Under the action of hexadecyl trimethyl ammonium bromide and ascorbic acid, copper ions generated by copper acetate are complexed on the surface of the gold nanosphere and generate CuSe with sodium hydroselenide, and the generated CuSe grows out a two-dimensional copper selenide nano disc in the tangential direction of the gold nanosphere under the auxiliary action of the hexadecyl trimethyl ammonium bromide to obtain the Au/CuSe tangential heterogeneous nano material. The Au/CuSe tangential heterogeneous nano material is prepared by using an all-water phase method, and the prepared heterogeneous nano material has a stable shape structure, an obvious double-plasmon coupling effect and excellent photocatalytic hydrogen production performance.
Further, the step S1 includes:
s1.1, mixing a chloroauric acid solution, a hexadecyl trimethyl ammonium bromide solution and a sodium borohydride solution for reaction to obtain a nano-gold seed solution;
s1.2, mixing a chloroauric acid solution, an ascorbic acid solution and a hexadecyl trimethyl ammonium bromide solution to obtain a first solution, adding the nano gold seed solution obtained in the step S1.1 into the first solution, adjusting the pH value to 1.3-11.7, and reacting to obtain the nano gold colloidal solution.
The method has the advantages that the obtained gold nanospheres are uniform and controllable in particle size, and the ratio of the seeds to the substances in the first solution can be controlled to produce the gold nanospheres with different sizes in the seed growth process.
Further, the sodium borohydride solution is a sodium borohydride ice-water mixture.
The method has the advantages that the reaction temperature is controlled to slow down the reaction rate, so that the seeds slowly grow, and the particle size of the gold nanospheres is uniform and controllable.
Further, when the volumes of the chloroauric acid solution, the cetyltrimethylammonium bromide and the sodium borohydride solution in the step S1.1 are 500 μ L, 8mL and 600 μ L respectively, the concentrations of the chloroauric acid solution, the cetyltrimethylammonium bromide and the sodium borohydride solution are 0.048-0.052M, 0.08-0.12M and 0.009-0.011M respectively, the reaction time is 2-2.5 hours, and stirring is performed at 1000 rpm in the reaction process.
Further, when the volumes of the nanogold seed solution, the chloroauric acid solution, the ascorbic acid solution and the hexadecyl trimethyl ammonium bromide solution in the step S1.2 are respectively 30 μ L, 6mL, 3.5mL and 30mL, the concentrations of the chloroauric acid solution, the ascorbic acid solution and the hexadecyl trimethyl ammonium bromide solution are respectively 4.5-5.5 mM, 8-16 mM and 0.17-0.23M, the reaction time is 1-2 h, after the reaction is finished, a reaction product is centrifuged at 10000rpm for 15min, and the precipitate is re-dispersed into deionized water.
The further scheme has the beneficial effect that the nano gold particles with the particle size of 18-22 nm can be obtained in a controlled manner.
Further, the preparation method of the sodium hydrogen selenide solution comprises the following steps: dissolving sodium borohydride in water, freezing at the temperature of 20-6-4 ℃ for 6-10 min, adding selenium powder into the sodium borohydride aqueous solution, and stirring until the selenium powder is completely dissolved to obtain the sodium selenide solution, wherein the molar ratio of the sodium borohydride to the selenium powder is (1.9-2.1): 1, the concentration of the sodium hydroselenide is 0.75-0.125M.
Further, the specific step of the step S3 is to cool the Au/CuSe tangential heterogeneous nano material aqueous solution, centrifuge the solution at 8000-10000 rpm for 5 minutes to obtain a solid product, alternately clean the solid product with deionized water and ethanol, and place the solid product in a forced air drying oven at 60-70 ℃ for 10-12 hours to obtain the Au/CuSe tangential heterogeneous nano material.
Further, the specific step of step S2 is: and (3) taking 5mL of the nano gold colloidal solution prepared in the step S1, adding 1mL of ascorbic acid, 1mL of hexamethylenetetramine, 1mL of hexadecyl trimethyl ammonium bromide, 60 MuL of sodium selenide and 600 MuL of copper acetate solution to obtain a second mixed solution, transferring the second mixed solution into a reaction container for packaging, placing the reaction container in a vacuum drying oven, vacuumizing, heating to 85-95 ℃, and reacting for 7.5-8.5 h, wherein the concentrations of the ascorbic acid, the hexamethylenetetramine solution, the hexadecyl trimethyl ammonium bromide solution, the sodium selenide and the copper acetate solution are 870-130 mM, 70-130 mM, 170-230 mM, 75-125 mM and 7-13 mM respectively.
The invention also provides the Au/CuSe tangential heterogeneous nano material prepared by the preparation method.
The Au/CuSe tangential heterogeneous nano material prepared by the method has a stable shape and structure, and the photocatalytic hydrogen production performance of the heterogeneous structure is enhanced by utilizing the double-plasmon coupling of the gold nanospheres and the copper selenide.
Drawings
FIG. 1 is a TEM photograph of Au/CuSe tangential heterogeneous nanomaterial prepared in example 3 of the present invention;
FIG. 2 is a transmission electron microscope photograph of a portion of the side of the Au/CuSe tangential heterogeneous nanomaterial prepared in example 3 of the present invention;
FIG. 3 shows the photocatalytic hydrogen generation rate of Au/CuSe tangential heterogeneous nanomaterial prepared in example 3, pure copper selenide and a mixture of Au and CuSe as catalysts under illumination respectively.
Detailed Description
The principles and features of this invention are described in connection with the drawings and the detailed description of the invention, which are set forth below as examples to illustrate the invention and not to limit the scope of the invention.
All the solutions below are aqueous solutions unless otherwise specified.
Example 1
(1) Preparation of Nanogold seed solution
Adding 8mL of 0.1M hexadecyl trimethyl ammonium bromide solution, 0.5mL of 0.05M chloroauric acid solution and 0.6mL of 0.01M sodium borohydride ice-water mixture into a test tube, reacting for 2h at normal temperature, stirring with a magnet during the reaction process, and setting a magnetic stirrer at 1000 revolutions per minute to obtain the nanogold seed solution.
(2) Preparation of Nanogold colloidal solution
Mixing 30mL of 0.2M hexadecyl trimethyl ammonium bromide, 6mL of 5mM chloroauric acid solution and 3.5mL of 0.01M ascorbic acid solution to obtain a first solution, adding 40 μ L of the nanogold seed solution obtained in the step (1) into the first solution, then adding 1mL of 1M sodium hydroxide to adjust the pH value to 11.3-11.7, placing the obtained reaction system in a biochemical incubator at 25-35 ℃ for reaction for 1h, centrifuging the product at 10000rpm for 15min after the reaction is finished, and re-dispersing the product into deionized water with the same volume to obtain a nanogold colloidal solution with the concentration of 45-55 nM, wherein the average particle size of nanogold is 20 nM.
By controlling the proportion of the seeds to the substances in the first solution, the nano gold particles with different sizes can be controlled and produced, and nano gold colloid solutions with the average particle diameters of 18nm and 22nm are prepared by the same method.
EXAMPLE 2 preparation of sodium Selenide
Weighing 75.66mg of sodium borohydride, dissolving in 10mL of deionized water, freezing at-4 ℃ for 8min, adding 78.96mg of selenium powder into the frozen sodium borohydride solution, continuously stirring until the selenium powder is completely dissolved to obtain a sodium selenide solution with the concentration of 0.1M, and preparing sodium selenide solutions with the concentrations of 75mM and 125mM respectively by adjusting the concentrations of the sodium borohydride and the selenium powder.
EXAMPLE 3 preparation of Au/CuSe tangential heterogeneous nanomaterial
5mL of the nanogold colloidal solution having a concentration of 50nM and an average particle diameter of 20nM prepared in example 1 were added with 1mL of ascorbic acid solution having a concentration of 0.1M, 1mL of hexamethyltetramine solution having a concentration of 0.1M and 1mL of cetyltrimethylammonium bromide solution having a concentration of 0.2M, then 60 mu L of sodium hydroselenide solution with the concentration of 0.1M and 600 mu L of copper acetate solution with the concentration of 10mM are added to obtain a second mixed solution, the second mixed solution is transferred into a test tube for packaging, the test tube is placed in a vacuum drying oven for vacuumizing and heating to 90 ℃ and keeping for 8 hours to obtain Au/CuSe tangential heterogeneous nano-material aqueous solution, and cooling the solid product to room temperature, centrifuging at 8000rpm for 5min to obtain a solid product, alternately cleaning the solid product with deionized water and ethanol, drying at 65 ℃ in an air-blast drying oven, and keeping for 12h to obtain the Au/CuSe tangential heterogeneous nano material.
FIG. 1 is a TEM photograph of the Au/CuSe tangential heterogeneous nanomaterial prepared in this example, showing that the average diameter of the Au nanospheres is about 20nm and the diameter of the CuSe nanodisks is about 45 nm.
Fig. 2 is a transmission electron microscope photograph of a portion of the side of the Au/CuSe tangential heterogeneous nanomaterial prepared in this example, where a portion of the side shows that the CuSe nanodisk is tangent to the Au nanospheres, and the thickness of the CuSe nanodisk is about 5.5 nm.
Example 4
5mL of the nanogold colloidal solution having a concentration of 55nM and an average particle diameter of 18nM prepared in example 1 were added with 1mL of ascorbic acid solution having a concentration of 0.13M, 1mL of hexamethyltetramine solution having a concentration of 0.13M and 1mL of cetyltrimethylammonium bromide solution having a concentration of 0.23M, then 60 mul of sodium hydroselenide solution with the concentration of 0.125M and 600 mul of copper acetate solution with the concentration of 13mM are added to obtain a second mixed solution, the second mixed solution is transferred into a test tube to be vacuumized and packaged, the test tube is placed in a vacuum drying oven and then heated to 95 ℃ and kept for 8.5h to obtain Au/CuSe tangential heterogeneous nano-material aqueous solution, and cooling the solid product to room temperature, centrifuging the solid product at 10000rpm for 5min to obtain a separated solid product, alternately cleaning the solid product by using deionized water and ethanol, drying the solid product in a forced air drying oven at 60 ℃ and keeping the temperature for 12h to obtain the Au/CuSe tangential heterogeneous nano material.
Example 5
5mL of the nanogold colloidal solution having a concentration of 45nM and an average particle diameter of 22nM prepared in example 1 were added with 1mL of ascorbic acid solution having a concentration of 0.07M, 1mL of hexamethyltetramine solution having a concentration of 0.07M and 1mL of cetyltrimethylammonium bromide solution having a concentration of 0.17M, then 60 mu L of sodium hydroselenide solution with the concentration of 0.075M and 600 mu L of copper acetate solution with the concentration of 7mM are added to obtain a second mixed solution, the second mixed solution is transferred into a test tube, is vacuumized and packaged, is placed in a vacuum drying oven and is heated to 85 ℃ and kept for 7.5 hours to obtain Au/CuSe tangential heterogeneous nano-material aqueous solution, and cooling the solid product to room temperature, centrifuging the solid product at 8000rpm for 5min to obtain a solid product, alternately cleaning the solid product by using deionized water and ethanol, drying the solid product in an air-blast drying oven at 70 ℃ and keeping the temperature for 10h to obtain the Au/CuSe tangential heterogeneous nano material.
Test examples
The Au/CuSe tangential heterogeneous nano-material prepared in the example 3, pure copper selenide (the other steps of the preparation method are the same as those of the example 2 except that 5mL of Au nanospheres are not added) and a mixture of Au and CuSe are respectively used as catalysts, and the hydrogen production rate of the Au/CuSe tangential heterogeneous nano-material under the illumination condition (the wavelength is more than 420nm) is compared.
When the mixture of Au and CuSe is used as a catalyst, the mass ratio of Au to CuSe is 1: 16.5 mixing.
The specific experimental process is as follows: 50mg of catalyst is taken and added into 50mL of mixed solution of sodium sulfide and sodium sulfite, wherein the concentration of the sodium sulfide is 0.35M, the concentration of the sodium sulfite is 0.25M, the solution is placed into a quartz reactor, the quartz reactor is installed on a commercial photocatalytic evaluation system, and a light source is a 300-watt xenon lamp and is provided with an ultraviolet cut-off filter (the wavelength is more than 420 nanometers). The temperature of the whole reaction system is kept by circulating cooling water, and the temperature of the circulating cooling water is set to be 2 ℃. The volume of hydrogen was monitored in real time by gas chromatography, and the volume of hydrogen produced was recorded every hour.
Results as shown in fig. 3, Au/CuSe tangential heterogeneous nanomaterial catalyzed reaction hydrogen production rate at 7 hours was 3.77 mmol/g, higher than pure CuSe (0.67 mmol/g) and Au and CuSe were directly mixed (0.82 mmol/g).
The Au/CuSe tangential heterogeneous nanomaterials prepared in examples 4 and 5 catalyzed reactions with 7 hours hydrogen production rates of 3.65 and 3.7 mmol/g, respectively, both higher than CuSe (0.67 mmol/g) and the Au and CuSe were directly mixed (0.82 mmol/g).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of Au/CuSe tangential heterogeneous nano material is characterized by comprising the following steps:
s1, preparing a nano gold colloidal solution in a hexadecyl trimethyl ammonium bromide system, wherein the particle size of gold nanospheres is 18-22 nm; the step S1 includes:
s1.1, mixing a chloroauric acid solution, a hexadecyl trimethyl ammonium bromide solution and a sodium borohydride solution for reaction to obtain a nano-gold seed solution;
s1.2, mixing a chloroauric acid solution, an ascorbic acid solution and a hexadecyl trimethyl ammonium bromide solution to obtain a first solution, adding the nano gold seed solution obtained in the step S1.1 into the first solution, adjusting the pH value to 11.3-11.7, and reacting to obtain a nano gold colloidal solution;
s2, preparing a sodium hydroselenide solution, taking the gold nanospheres as a growth substrate, taking sodium hydroselenide and copper acetate as precursors, taking ascorbic acid as a reducing agent, taking hexadecyl trimethyl ammonium bromide as a surfactant, and reacting in vacuum in the presence of hexamethylenetetramine to grow a two-dimensional copper selenide nanodisk in the tangential direction of the gold nanospheres to obtain an Au/CuSe tangential heterogeneous nanomaterial aqueous solution, wherein the concentrations of the gold nanospheres, the sodium hydroselenide, the copper acetate, the ascorbic acid, the hexamethylenetetramine and the hexadecyl trimethyl ammonium bromide in a reaction system are respectively 25.96-31.76 nM, 0.52-0.87 mM, 0.48-0.90 mM, 8.08-15.01 mM and 19.63-26.56 mM, the reaction temperature is 85-95 ℃, and the reaction time is 7.5-8.5 h;
s3, centrifuging the Au/CuSe tangential heterogeneous nano material aqueous solution to obtain a solid product, and cleaning and drying the solid product to obtain the Au/CuSe tangential heterogeneous nano material.
2. The method for preparing Au/CuSe tangential heterogeneous nano-material according to claim 1, wherein the sodium borohydride solution is a sodium borohydride ice-water mixture.
3. The method for preparing Au/CuSe tangential heterogeneous nano-material according to claim 2, wherein when the volumes of the chloroauric acid solution, the cetyltrimethylammonium bromide and the sodium borohydride solution in the step S1.1 are 500 μ L, 8mL and 600 μ L respectively, the concentrations of the chloroauric acid solution, the cetyltrimethylammonium bromide and the sodium borohydride solution are 0.048-0.052M, 0.17-0.23M and 0.009-0.011M respectively, the reaction time is 2-2.5 h, and the stirring is performed at 1000 rpm during the reaction process.
4. The method for preparing Au/CuSe tangential heterogeneous nano-material according to claim 3, wherein in the step S1.2, when the volumes of the nanogold seed solution, the chloroauric acid solution, the ascorbic acid solution and the cetyltrimethyl ammonium bromide solution are 30 μ L, 6mL, 3.5mL and 30mL respectively, the concentrations of the chloroauric acid solution, the ascorbic acid solution and the cetyltrimethyl ammonium bromide are 4.5-5.5 mM, 8-16 mM and 0.17-0.23M respectively, the reaction time is 1-2 h, after the reaction is completed, the reaction product is centrifuged at 10000rpm for 15min, and the precipitate is re-dispersed into deionized water.
5. The method for preparing Au/CuSe tangential heterogeneous nano-material according to claim 1, wherein the method for preparing the sodium hydroselenide solution comprises the following steps: dissolving sodium borohydride in water, freezing at the temperature of-6 to-4 ℃ for 6 to 10min, adding selenium powder into the sodium borohydride aqueous solution, and stirring until the selenium powder is completely dissolved to obtain the sodium selenide solution, wherein the molar ratio of the sodium borohydride to the selenium powder is 1.9 to 2.1: 1, the concentration of the sodium hydroselenide is 0.75-0.125M.
6. The method for preparing the Au/CuSe tangential heterogeneous nano material as claimed in any one of claims 1 to 5, wherein the specific step of the step S3 is to cool the aqueous solution of the Au/CuSe tangential heterogeneous nano material to room temperature, then centrifuge the solution at 8000 to 10000rpm for 5 minutes to obtain a solid product, alternately clean the solid product with deionized water and ethanol, and place the solid product in a forced air drying oven at 60 to 70 ℃ for 10 to 12 hours to obtain the Au/CuSe tangential heterogeneous nano material.
7. The method for preparing Au/CuSe tangential heterogeneous nano-material according to any one of claims 1 to 5, wherein the step S2 comprises the following specific steps: taking 5mL of the nano gold colloidal solution prepared in the step S1, adjusting the concentration to 45-55 nM, adding 1mL of ascorbic acid, 1mL of hexamethylenetetramine, 1mL of hexadecyl trimethyl ammonium bromide, 60 muL of sodium selenide hydride solution and 600 muL of copper acetate solution to obtain a second mixed solution, transferring the second mixed solution to a reaction container for packaging, placing the second mixed solution in a vacuum drying box for vacuumizing, heating to 85-95 ℃ for reaction for 7.5-8.5 h, wherein the concentrations of the ascorbic acid, the hexamethylenetetramine solution, the hexadecyl trimethyl ammonium bromide solution, the sodium selenide hydride solution and the copper acetate solution are 870-130 mM, 70-130 mM, 170-230 mM, 75-125 mM and 7-13 mM respectively.
8. An Au/CuSe tangential heterogeneous nano material, which is characterized by being prepared by the preparation method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910747931.0A CN110479319B (en) | 2019-08-14 | 2019-08-14 | Au/CuSe tangential heterogeneous nano material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910747931.0A CN110479319B (en) | 2019-08-14 | 2019-08-14 | Au/CuSe tangential heterogeneous nano material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110479319A CN110479319A (en) | 2019-11-22 |
| CN110479319B true CN110479319B (en) | 2022-05-03 |
Family
ID=68551055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910747931.0A Active CN110479319B (en) | 2019-08-14 | 2019-08-14 | Au/CuSe tangential heterogeneous nano material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110479319B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111790406B (en) * | 2020-07-20 | 2022-04-12 | 济南大学 | Preparation method of gold-copper selenide-cobalt-nickel layered double hydroxide composite paper |
| WO2022211739A1 (en) * | 2021-03-31 | 2022-10-06 | Agency For Science, Technology And Research | Ambient scalable synthesis of surfactant-free nanostructured chalcogenide particles for near room-temperature thermoelectric applications |
| CN114122388B (en) * | 2021-11-16 | 2024-04-02 | 信阳师范学院 | CuSe nano material for sodium ion battery and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005052996A2 (en) * | 2003-11-19 | 2005-06-09 | William Marsh Rice University | Methods and materials for cdse nanocrystal synthesis |
| CN1884432A (en) * | 2006-07-07 | 2006-12-27 | 中国科学技术大学 | Au/CdSe heterostructure quantum point and its preparation method |
| CN102268262A (en) * | 2011-05-25 | 2011-12-07 | 云南大学 | Method for synthesizing Pt: ZnSe(S) alloy nano crystal by aqueous phase process |
| WO2011163299A2 (en) * | 2010-06-22 | 2011-12-29 | University Of Florida Research Foundation, Inc. | Nanocrystalline copper indium diselenide (cis) and ink-based alloys absorber layers for solar cells |
| CN102500758A (en) * | 2011-09-29 | 2012-06-20 | 厦门大学 | Core shell nanometer crystal of gold and copper-indium-diselenide and preparation method of core shell nanometer crystal |
| CN105618781A (en) * | 2016-01-02 | 2016-06-01 | 华东理工大学 | Preparation method of Au@Cu2-xSe cage-like core-shell nanostructures |
| CN107737598A (en) * | 2017-09-25 | 2018-02-27 | 唐明睿 | A kind of Cu1.8Se/CuAgSe composite photocatalyst materials and preparation method thereof |
| CN109019532A (en) * | 2018-08-28 | 2018-12-18 | 曲阜师范大学 | A kind of tetragonal phase two dimension CuFeSe2The liquid phase preparation process of nanometer sheet crystal |
-
2019
- 2019-08-14 CN CN201910747931.0A patent/CN110479319B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005052996A2 (en) * | 2003-11-19 | 2005-06-09 | William Marsh Rice University | Methods and materials for cdse nanocrystal synthesis |
| CN1884432A (en) * | 2006-07-07 | 2006-12-27 | 中国科学技术大学 | Au/CdSe heterostructure quantum point and its preparation method |
| WO2011163299A2 (en) * | 2010-06-22 | 2011-12-29 | University Of Florida Research Foundation, Inc. | Nanocrystalline copper indium diselenide (cis) and ink-based alloys absorber layers for solar cells |
| CN102268262A (en) * | 2011-05-25 | 2011-12-07 | 云南大学 | Method for synthesizing Pt: ZnSe(S) alloy nano crystal by aqueous phase process |
| CN102500758A (en) * | 2011-09-29 | 2012-06-20 | 厦门大学 | Core shell nanometer crystal of gold and copper-indium-diselenide and preparation method of core shell nanometer crystal |
| CN105618781A (en) * | 2016-01-02 | 2016-06-01 | 华东理工大学 | Preparation method of Au@Cu2-xSe cage-like core-shell nanostructures |
| CN107737598A (en) * | 2017-09-25 | 2018-02-27 | 唐明睿 | A kind of Cu1.8Se/CuAgSe composite photocatalyst materials and preparation method thereof |
| CN109019532A (en) * | 2018-08-28 | 2018-12-18 | 曲阜师范大学 | A kind of tetragonal phase two dimension CuFeSe2The liquid phase preparation process of nanometer sheet crystal |
Non-Patent Citations (1)
| Title |
|---|
| Growth behavior of Au/Cu2-xS hybrids and their Plasmon-enhanced dual-functional catalytic activity;Liang Ma et al.;《CRYSTENGCOMM》;20190809;第21卷;第5610-5617页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110479319A (en) | 2019-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110479319B (en) | Au/CuSe tangential heterogeneous nano material and preparation method thereof | |
| JP6570688B2 (en) | Synthesis of metal oxide nanoparticles from molecular cluster compounds | |
| US6855204B2 (en) | High yield method for preparing silicon nanocrystals with chemically accessible surfaces | |
| CN108246331B (en) | ZnS micron composite material modified by graphene nitrogen carbide quantum dots and preparation method and application thereof | |
| CN108620601B (en) | Method for preparing flaky Cu nanocrystalline at room temperature | |
| CN107433203B (en) | Z-Scheme composite system, preparation method and application | |
| CN109110795B (en) | Copper-based nano/micron composite particles and preparation method and application thereof | |
| Ma et al. | Novel synthesis and characterization of bismuth nano/microcrystals with sodium hypophosphite as reductant | |
| He et al. | Low‐temperature solvothermal synthesis of ZnO quantum dots | |
| CN105586028A (en) | Preparing method for CdSe@CdS core-shell structure quantum dots | |
| Duan et al. | Characterization of ZnSe microspheres synthesized under different hydrothermal conditions | |
| CN110508297B (en) | Pt-modified Au/CuSe tangential heterogeneous nano material and preparation method thereof | |
| CN115121260A (en) | Nano gold-cuprous oxide heterojunction and preparation method and application thereof | |
| CN111054419B (en) | For CO 2 Reduced semiconductor/g-C 3 N 4 Photocatalyst and preparation method thereof | |
| CN110078116B (en) | Perovskite CsPbBr3Quantum dot and preparation method and application thereof | |
| CN112777646A (en) | Preparation method of sea urchin-shaped basic cobalt carbonate | |
| CN110586132A (en) | Half-core-shell Au/Cu2-xS heterogeneous nano material and preparation method thereof | |
| CN110368954B (en) | Cu-Ag-In-Zn-S quantum dot photocatalyst prepared by hydrothermal doping method and application thereof | |
| Liu et al. | Growth mechanism of Ag 2 S nanocrystals in a nonpolar organic solvent | |
| CN115400753B (en) | Preparation method of gold-silver core-shell nano bipyramid-cerium dioxide composite material | |
| CN113415821B (en) | Hollow Zn x Cd 1-x Preparation method and application of S solid solution nanosphere | |
| Wang et al. | Synthesis and characterization of CdTe quantum dots by one-step method | |
| Mlambo et al. | Influence of temperature and precursor concentration on the synthesis of HDA-capped Ag2Se nanoparticles | |
| CN111036935B (en) | Gap-adjustable Au layer, core of AgAu layer and CdS shell nano material, and preparation method and application thereof | |
| CN114538388B (en) | Preparation method of zinc selenide nanowire with controllable composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |