CN112774684B - Graphene ball-loaded transition metal quantum dot composite material and preparation method thereof - Google Patents
Graphene ball-loaded transition metal quantum dot composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 239000002096 quantum dot Substances 0.000 title claims abstract description 59
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 50
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052786 argon Inorganic materials 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 12
- -1 transition metal acetate Chemical class 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 7
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 7
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- 238000005844 autocatalytic reaction Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000007040 multi-step synthesis reaction Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/394—
-
- B01J35/40—
-
- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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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
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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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a graphene ball loaded transition metal quantum dot composite material and a preparation method thereof, and belongs to the field of functional nano materials. The invention solves the technical problems that the preparation process of the graphene/transition metal quantum dot composite material is complex, the dispersity of the quantum dots is difficult to control, and the cost is high. The graphene ball loaded transition metal quantum dot composite material is obtained by carrying out heat treatment on transition metal acetate in hydrogen-argon mixed gas, wherein quantum dots are good in dispersity, uniform in size, large in specific surface area, high in conductivity, short in production period, low in cost, strong in repeatability and capable of being prepared in a large scale, and therefore the graphene ball loaded transition metal quantum dot composite material has a wide application prospect in the field of catalysis.
Description
Technical Field
The invention belongs to the field of functional nano materials, and particularly relates to a graphene sphere loaded transition metal quantum dot composite material and a preparation method thereof.
Background
Graphene is used as a star material in a carbon material family, and becomes an important research object in the fields of chemistry, materials, physics and the like due to excellent physicochemical properties of graphene, and compared with an original two-dimensional graphene sheet, a graphene sphere has a larger specific surface area and a more stable structure, so that the graphene sphere has a wide application prospect in the field of electrochemical energy storage. On the other hand, the transition metal quantum dots have unique properties due to quantum effects, exhibit many different physicochemical properties from those of macroscopic materials, and show excellent performance in the field of energy catalytic materials. The graphene ball/transition metal quantum dot composite structure is constructed, so that the synergistic effect of graphene and quantum dots can be fully exerted, and the electrochemical performance is improved.
However, in the process of preparing the graphene sphere loaded transition metal quantum dot composite material, multi-step synthesis is often required, the process is complex, the dispersibility of the quantum dots is often difficult to control, and the cost is high. Therefore, the graphene ball-loaded transition metal quantum dot composite material with specific morphology and high specific surface area is prepared in a large-scale controllable manner by utilizing a simple process and realizing good dispersion of quantum dots in the graphene ball, and has extremely important theoretical value and practical significance for development of high-performance electrocatalysts.
Disclosure of Invention
The invention aims to solve the technical problems that the preparation process of the graphene/transition metal quantum dot composite material is complex, the dispersity of the quantum dots is difficult to control, and the cost is high.
In order to solve the technical problem, the invention discloses a preparation method of a graphene ball loaded transition metal quantum dot composite material, which comprises the following steps: taking a proper amount of transition metal acetate, taking acetate in the acetate as a carbon source, taking transition metal ions as a catalyst, and carrying out pyrolysis autocatalytic reaction at a certain temperature to obtain the graphene ball loaded transition metal quantum dot composite material.
The heat treatment process specifically comprises the steps of heating to 90-110 ℃ in a hydrogen-argon mixed gas, preserving heat for 1-2 hours, then heating to 300-400 ℃, preserving heat for 1-2 hours, then heating to 800-1200 ℃, preserving heat for 2-3 hours, then cooling to room temperature, and collecting a product, namely the graphene ball loaded transition metal quantum dot composite material.
Wherein the transition metal acetate is one of nickel acetate tetrahydrate and copper acetate monohydrate.
Wherein, in the hydrogen-argon mixed gas, the volume fraction of argon is 70-90%, and the volume fraction of hydrogen is 10-30%.
Wherein the total flow of the hydrogen-argon mixed gas is 180-220 sccm. sccm is the volume flow unit of gas, i.e., standard state ml/min.
Wherein the heating rate and the cooling rate are 4-6 ℃/min in the heat treatment process.
In addition, in view of the fact that the graphene/transition metal quantum dot composite structure can fully exert the synergistic effect of graphene and quantum dots and improve the electrochemical performance, the invention also discloses a graphene sphere loaded transition metal quantum dot composite material which is composed of graphene spheres and transition metal quantum dots loaded on the graphene spheres.
Wherein the transition metal quantum dots are one of nickel quantum dots and copper quantum dots.
Wherein the particle size distribution of the transition metal quantum dots is 1-5 nm.
Wherein the average grain size of the transition metal quantum dots is 2.9nm.
The graphene spherical wall is formed by assembling graphene in situ.
Wherein the number of graphene layers on the graphene ball wall is within 10.
Meanwhile, the invention also discloses the graphene ball loaded transition metal quantum dot composite material prepared by the process.
The invention has the following advantages and beneficial effects:
the graphene ball/transition metal quantum dot composite material is composed of graphene balls with a hollow structure and transition metal quantum dots uniformly dispersed on the graphene, wherein the quantum dots are good in dispersibility and uniform in size, and the walls of the graphene balls are formed by assembling graphene within 10 layers in situ;
the composite material prepared by the invention has large specific surface area, high conductivity, performance close to that of a commercial platinum-carbon catalyst, and wide application prospect in the field of catalysis;
the preparation process of the composite material is simple and easy to operate, low in cost and capable of realizing large-scale preparation.
Drawings
The accompanying drawings, which are included to provide a further understanding of and explain embodiments of the invention, are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a transmission electron micrograph of the dispersion of nickel quantum dots on the graphene spherical wall according to the present invention;
FIG. 2 is a graph showing the oxygen reduction catalytic performance of the composite material prepared in examples 1 and 2 and a commercial platinum-carbon catalyst.
Detailed Description
In the prior art, at least two raw materials are often needed in the process of constructing the graphene/transition metal quantum dot composite structure, multi-step synthesis is involved, the process is complex, the dispersibility of the quantum dots is often difficult to control, and the cost is high. According to the invention, through the screening of raw materials and the design of a process, a single raw material is adopted, and the transition metal quantum dots can be loaded while graphene spheres are generated in situ through a simple heat treatment process, so that the graphene/transition metal quantum dot composite material is obtained.
According to the invention, transition metal acetate is adopted as a reaction raw material, acetate in the acetate is used as a carbon source, transition metal ions in the acetate are used as a catalyst, the catalyst catalyzes the carbon source to generate graphene in a heat treatment process, the graphene is further assembled in situ to form a graphene spherical wall, and the metal ions are uniformly loaded on the graphene in a quantum dot form, so that the composite material of the graphene sphere loaded with the transition metal quantum dots is obtained.
The specific heat treatment mode can be adjusted according to the types of different transition metal acetates, the aim is to enable the metal ions to catalyze the carbon source to generate graphene through heat treatment, the graphene is assembled in situ to form a graphene spherical wall, and the metal ions are uniformly loaded on the graphene in the form of quantum dots.
Preferably, the preparation method of the graphene sphere loaded transition metal quantum dot composite material can be carried out according to the following steps: weighing a proper amount of transition metal acetate in a crucible, covering the crucible, placing the crucible in a tubular furnace, heating the crucible in a hydrogen-argon mixed gas to 100 ℃, preserving the heat for 1-2 h, then heating the crucible to 300-400 ℃, preserving the heat for 1-2 h, then heating the crucible to 800-1200 ℃, preserving the heat for 2-3 h, then cooling the crucible to room temperature, and collecting a product, namely the graphene ball loaded transition metal quantum dot composite material.
Because copper and nickel have good catalytic performance, the transition metal acetate adopts one of tetrahydrate nickel acetate and monohydrate copper acetate as preferable.
Preferably, the volume of the transition metal acetate powder is half of the capacity of a crucible, which is one of an alumina crucible and a graphite crucible.
In the test of the invention, the volume fraction of argon and hydrogen in the mixed gas has influence on the size of the catalyst, and preferably, the volume fraction of argon in the hydrogen-argon mixed gas is 70-90%, and the volume fraction of hydrogen is 10-30%.
In order to ensure better stability of the gas flow, the total flow rate of the hydrogen-argon mixture is preferably 180 to 220sccm.
Preferably, the heating rate and the cooling rate in the heat treatment process are 5 ℃/min.
The invention also discloses a graphene ball loaded transition metal quantum dot composite material, which consists of the graphene ball and the transition metal quantum dot loaded on the graphene ball.
Preferably, the transition metal quantum dot is one of a nickel quantum dot and a copper quantum dot.
Preferably, the particle size distribution of the transition metal quantum dots is 1-5 nm; the average particle size of the transition metal quantum dots is 2.9nm.
Preferably, the graphene spherical wall is formed by in-situ assembling graphene; the number of graphene layers on the graphene spherical wall is within 10 layers.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
Weighing nickel acetate tetrahydrate in an alumina crucible, wherein the volume ratio of the nickel acetate tetrahydrate is one half of the volume of the crucible, and capping the crucible; the crucible was placed in a tube furnace under hydrogen argon (H) mixture 2 Heating to 100 ℃ at a heating rate of 5 ℃/min in a volume ratio of 1/Ar of 1); then heating to the temperature at the heating rate of 5 ℃/minKeeping the temperature at 300 ℃ for 1h; heating to 900 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2h; and then, cooling to room temperature at a cooling rate of 5 ℃/min, collecting a product, namely the graphene ball-loaded nickel quantum dot composite material, wherein a transmission photo of the distribution condition of the nickel quantum dots on the graphene is shown in figure 1.
The graphene ball-supported nickel quantum dot composite material prepared in the embodiment 1, absolute ethyl alcohol and a perfluorinated sulfonic acid solution are mixed, ink is formed after uniform ultrasonic dispersion, the ink is dripped onto a glassy carbon electrode, the glassy carbon electrode is naturally dried and then installed on a rotating disk electrode, one end on which the ink is dripped is immersed into electrolyte, the electrolyte adopts 0.1M KOH solution and oxygen is always introduced to enable the electrolyte to be in an oxygen saturation state, an electrochemical workstation is adopted to test a polarization curve (LSV), the test voltage range is-0.9-0.3V, and the rotating speed of the rotating disk electrode is 1600rpm. The catalytic performance results are shown in FIG. 2, and it can be seen that the limiting current density (4.5) of the sample prepared at 900 ℃ is close to that of the commercial platinum-carbon catalyst (5.5), and the method has a good application prospect.
Example 2
Weighing nickel acetate tetrahydrate in an alumina crucible, wherein the volume ratio of the nickel acetate tetrahydrate is one half of the volume of the crucible, and capping the crucible; the crucible was placed in a tube furnace under hydrogen argon (H) mixture 2 Heating to 100 ℃ at a heating rate of 5 ℃/min in a volume ratio of 1/Ar of 1); then heating to 300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1h; heating to 1100 deg.C at a heating rate of 5 deg.C/min, and maintaining for 2 hr; and then, cooling to room temperature at a cooling rate of 5 ℃/min, and collecting a product, namely the graphene ball-loaded nickel quantum dot composite material.
The graphene ball-supported nickel quantum dot composite material prepared in the embodiment 2, absolute ethyl alcohol and a perfluorinated sulfonic acid solution are mixed, ink is formed after uniform ultrasonic dispersion, the ink is dripped onto a glassy carbon electrode, the glassy carbon electrode is naturally dried and then installed on a rotating disk electrode, one end on which the ink is dripped is immersed into electrolyte, the electrolyte adopts 0.1M KOH solution and oxygen is always introduced to enable the electrolyte to be in an oxygen saturation state, an electrochemical workstation is adopted to test a polarization curve (LSV), the test voltage range is-0.9-0.3V, and the rotating speed of the rotating disk electrode is 1600rpm. The catalytic performance results are shown in figure 2.
Example 3
Weighing copper acetate monohydrate in an alumina crucible, wherein the volume ratio of the copper acetate monohydrate is one half of the volume of the crucible, and covering the crucible; the crucible was placed in a tube furnace under hydrogen argon (H) mixture 2 Heating to 100 ℃ at a heating rate of 5 ℃/min in a volume ratio of Ar to 2); then heating to 300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1h; heating to 800 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2h; and then, cooling to room temperature at a cooling rate of 5 ℃/min, and collecting a product, namely the graphene ball-loaded copper quantum dot composite material.
Example 4
Weighing monohydrate copper acetate in a graphite crucible, wherein the volume ratio of the monohydrate copper acetate is one half of the volume of the crucible, and covering the crucible; the crucible was placed in a tube furnace under hydrogen argon (H) mixture 2 Heating to 100 ℃ at a heating rate of 5 ℃/min in a volume ratio of Ar to 2); then heating to 300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1h; heating to 1000 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2h; and then, cooling to room temperature at a cooling rate of 5 ℃/min, and collecting a product, namely the graphene ball-loaded copper quantum dot composite material.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. The preparation method of the graphene ball loaded transition metal quantum dot composite material is characterized by comprising the following steps: taking a proper amount of transition metal acetate, taking acetate in the acetate as a carbon source, taking transition metal ions as a catalyst, and carrying out pyrolysis autocatalytic reaction at a certain temperature to obtain the graphene ball loaded transition metal quantum dot composite material; the transition metal acetate is one of nickel acetate tetrahydrate and copper acetate monohydrate;
heating the reaction raw materials in a hydrogen-argon mixed gas to 90-110 ℃, preserving heat for 1-2h, then heating to 300-400 ℃, preserving heat for 1-2h, then heating to 800-1200 ℃, preserving heat for 2-3h, then cooling to room temperature, and collecting a product, namely the graphene ball loaded transition metal quantum dot composite material;
in the hydrogen-argon mixed gas, the volume fraction of argon is 70 to 90 percent, and the volume fraction of hydrogen is 10 to 30 percent; the total flow of the hydrogen-argon mixed gas is 180 to 220sccm.
2. The preparation method of the graphene sphere-supported transition metal quantum dot composite material according to claim 1, wherein the preparation method comprises the following steps: the heating rate and the cooling rate in the heat treatment process are 4-6 ℃/min.
3. The graphene sphere-supported transition metal quantum dot composite material prepared by the preparation method of any one of claims 1 to 2.
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| CN106006617B (en) * | 2016-05-25 | 2018-04-13 | 广东石油化工学院 | A kind of preparation method and applications of graphene hollow nano cages |
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| Copper nanodot-embedded graphene urchins of nearly full-spectrum solar absorption and extraordinary solar desalination;Xu Jijian 等;《NANO ENERGY》;20181130;第53卷;第425-431页 * |
| De Jesus Juan C. 等.Size tunable carbon-encapsulated nickel nanoparticles synthesized by pyrolysis of nickel acetate tetrahydrate.《Journal of Analytical and Applied Pyrolysis》.2018,第130卷第334-335页3.2、图3，第336页左栏第1段、图4. * |
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