CN118321542A - Size-controllable high-dispersion ultra-small nanocluster and preparation method and application thereof - Google Patents
Size-controllable high-dispersion ultra-small nanocluster and preparation method and application thereof Download PDFInfo
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- 239000006185 dispersion Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003607 modifier Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 9
- 239000003463 adsorbent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 3
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010411 electrocatalyst Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 claims description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
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- 238000005470 impregnation Methods 0.000 abstract description 2
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- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 2
- 150000004706 metal oxides Chemical class 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229910003310 Ni-Al Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
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- 238000003917 TEM image Methods 0.000 description 4
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- 150000001412 amines Chemical class 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of nano materials and heterogeneous catalysis, and particularly relates to a size-controllable high-dispersion ultra-small nanocluster, and a preparation method and application thereof. The preparation method comprises the following steps: and (3) taking cyclohexane and ethanol as solvents, adding excessive surface modifier and oxide carrier, performing ultrasonic dispersion, removing the solvent by a rotary evaporator, adsorbing for a period of time at high temperature, controlling the content of the surface modifier by washing with a proper amount of cyclohexane, drying, mixing with metal precursor salt, and performing ball milling and calcination to obtain the nano-porous metal oxide. The preparation method adopts a mode of liquid phase pretreatment and solid phase combination, so that the prepared ultra-small nanocluster with controllable size and high dispersion has the advantages of controllable size and high dispersion degree, and solves the problems of uneven size, low dispersion degree, easy agglomeration and the like of the loaded metal oxide in the synthesis process of the traditional liquid phase precipitation method, thermal decomposition method, sol-gel method, solution impregnation method and the like.
Description
Technical Field
The invention belongs to the field of nano materials and heterogeneous catalysis, and particularly relates to a size-controllable high-dispersion ultra-small nanocluster, and a preparation method and application thereof.
Background
The metal nanocluster with the nanometer size smaller than 100nm has unique electronic, magnetic, optical and chemical properties, while the cluster with the nanometer size smaller than 3nm has quantum size effect and high specific surface area, and has great significance in the field of heterogeneous catalysis.
The current method for synthesizing nanoclusters is mainly based on a chemical method and a method for re-exposing the surface of the nanoclusters, but has serious problems such as severe blocking of the outer surface of the catalyst by a coating agent generally used in a wet chemical method; heat treatment, oxidation treatment, etc. to re-expose the nanocluster surfaces typically results in irreversible changes in nanocluster size and morphology. There are also some finer methods to synthesize nanoclusters but are only suitable for synthesis of laboratory grade products and cannot be prepared on a large scale.
Therefore, the technical scheme of the invention is provided based on the above.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a concept of a solid state 'anchoring' strategy for synthesizing the size-controllable high-dispersion ultra-small nanoclusters. Specifically, the interaction between the surface modifier and the oxide support is enhanced by lewis acid-based interactions. The anchored surface modifier molecules act as complexing agents during subsequent syntheses, further capturing and dispersing the acetylacetonate metal salt complex during solid state ball milling. The mechanical ball milling process enhances the interaction between the metal cations and the oxide support in addition to providing shear forces to disperse the metal precursor salt. Thus, ni which is highly dispersed even after calcination in 500℃air, maintains an ultra-small size of 6.5nm even under high-temperature calcination conditions of 750 DEG C
The invention provides a preparation method of a size-controllable high-dispersion ultra-small nanocluster, which comprises the following steps:
(1) Adding a surface modifier and an oxide into a solvent for ultrasonic dispersion to obtain a dispersion liquid;
(2) Spin-evaporating the dispersion liquid to remove the solvent, and completely adsorbing the surface modifier and the oxide under the heating condition to obtain a spin-evaporated product;
(3) Washing the rotary steaming material, and sequentially centrifuging and drying to obtain a pretreatment oxide;
(4) And mixing the pretreated oxide with metal precursor salt, and then sequentially ball-milling and calcining to obtain the size-controllable high-dispersion ultra-small nanocluster.
Preferably, in the step (1), the surface modifier is one of oleylamine, oleic acid, sodium oleate, glycerin, polyethylene glycol, octadecanethiol, octadecene, and cetyltrimethylammonium bromide;
And/or the oxide is one of alumina, titanium dioxide, cerium dioxide, silicon dioxide, zirconium oxide, magnesium oxide, ferric oxide and zinc oxide;
And/or the solvent is cyclohexane and ethanol.
Preferably, the volume ratio of the cyclohexane to the ethanol is 0.3-0.5:1;
and/or the mol ratio of the oleylamine to the alumina is 0.5-0.9:1.
Preferably, in step (2), the surface modifier is fully adsorbed with the oxide at 70-100 ℃.
Preferably, in step (3), the spin-on is washed with cyclohexane.
Preferably, in the step (4), the metal precursor salt is one or a combination of two of acetylacetonate and acetate;
and/or the molar ratio of the metal precursor salt to the oxide is 0.005-0.1:1;
And/or the ball milling time is 0.25-1 h;
and/or the calcining temperature is 350-800 ℃ and the calcining time is 1-4 h.
Preferably, the acetylacetonate includes platinum acetylacetonate, copper acetylacetonate, nickel acetylacetonate, palladium acetylacetonate, rubidium acetylacetonate, rhodium acetylacetonate, cerium acetylacetonate, and lanthanum acetylacetonate;
And/or the ball mill adopted in the ball milling process is a planetary ball mill, a high-energy ball mill, a three-dimensional high-speed vibration ball mill (MSK-SFM-3) or manual grinding.
Based on the same technical conception, the invention also provides the ultra-small nanocluster with controllable size and high dispersion obtained by the preparation method.
Based on the same technical conception, another scheme of the invention is to provide an application of the size-controllable high-dispersion ultra-small nanoclusters in preparing heterogeneous thermal catalysts, electrocatalysts, photocatalysts and adsorbents.
The beneficial effects of the invention are as follows:
(1) The invention adopts a preparation mode of liquid phase and solid phase combination to prepare the ultra-small nanoclusters with controllable size and high dispersion, and uses long-chain organic matters as a carrier surface modifier to anchor the surface modifier and an oxide carrier together under the interaction of Lewis acid (Al-OH and NH 2 -R). Under the action of solid-phase ball milling, metal precursor salt is dissolved into crystal lattices of the oxide carrier, so that uniform mixing of the oxide carrier and the metal precursor salt is realized, then a surface modifier existing in the calcining process plays a role, the dispersibility of the nanoclusters is increased, excessive growth of the nanoclusters is limited, and the size-controllable high-dispersion ultra-small nanoclusters are obtained. The preparation method solves the problems of uneven size, larger particles, low dispersity and the like of the size-controllable high-dispersion nanoclusters in the existing synthesis processes of a liquid phase precipitation method, an impregnation method, a thermal decomposition method, a sol-gel method and the like, and the prepared nanoclusters also have certain hydrophobic capacity and have unexpected use in some reactions with water. In addition, the preparation method is simple, high in preparation efficiency, low in energy consumption, capable of achieving industrial amplification synthesis and suitable for industrial mass production.
(2) The size-controllable high-dispersion ultra-small nanocluster prepared by the method has the advantages of uniform size, controllable size, high dispersity, hydrophobicity, minimum particle size of 1nm, controllable shape and environmental friendliness; can be applied to the fields of heterogeneous thermal catalysts, electrocatalysts, photocatalysts, adsorbents and the like.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a transmission electron micrograph and a mapping photograph of 1% -Ni-Al 2O3 -OAm-500 obtained in example 1.
FIG. 2 is a graph of the hydrophobic angle test at various stages in the preparation of 1% -Ni-Al 2O3 -OAm-500 from example 1.
FIG. 3 is a transmission electron micrograph and a mapping photograph of 5% -Ni-Al 2O3 -OAm-750 obtained in example 1.
FIG. 4 is a transmission electron micrograph and a mapping photograph of 1% -Pt-Al 2O3 -OAm-500 obtained in example 2.
FIG. 5 is a transmission electron micrograph and a mapping photograph of 1% -Cu-SiO 2 -OAm-500 obtained in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Example 1
The embodiment provides a preparation method of a size-controllable high-dispersion ultra-small nanocluster, which comprises the following steps:
2g of Al 2O3 (19.62 mmol) and 5mL (15.48 mmol) of oleylamine were added to a flask containing 20mL of cyclohexane and 50mL of ethanol, and the mixture was subjected to ultrasonic dispersion for 30min, the solvents cyclohexane and ethanol were removed by using a rotary evaporator, and after sealing, the mixture was placed in a 100 ℃ oven to allow alumina to fully absorb oleylamine for 12h. The excess oil amine was removed by washing with 50mL of cyclohexane, centrifuging, drying, and placing 21.8mg of nickel acetylacetonate and pretreated alumina into a 50mL stainless steel ball mill tank containing 4 large stainless steel balls having a diameter of 20mm and 12 small stainless steel balls having a diameter of 10 mm. The ball milling pot was sealed and transferred to a three-dimensional high-speed vibratory ball mill (MSK-SFM-3), and the ball milling was run for 0.5h.
Then calcining at 500 ℃ for 2 hours at a heating rate of 5 ℃/min, and designating the prepared sample as 1% -Ni-Al 2O3 -OAm-500 according to the content, the adsorbent and the calcining temperature.
The resulting "1% -Ni-Al 2O3 -OAm-500" was reduced at 500℃under a 5% H 2/Ar atmosphere (5 ℃ C./min) for 2 hours, and subjected to a transmission electron microscope test and EDS (ENERGY DISPERSIVE Spectrometer) test, as shown in FIG. 1.
As can be seen from fig. 1, the Al 2O3 substrate after hydrogen reduction was free of nickel particles after calcination at 500 ℃ for 2 hours using OAm anchor method. High angle annular dark field scanning transmission electron microscopy (HADDF) imaging is then performed at the same location. However, no significant nickel particles were observed. Ni was found to be very uniformly dispersed over Al 2O3 by EDS and no agglomeration occurred.
From the hydrophobic angle experiment in fig. 2, OAm has been found that the application of OAm changes the catalyst from hydrophilic to hydrophobic, which provides application prospect for the application of the catalyst in water resistance.
Subsequently, a high temperature anti-agglomeration experiment test was performed on Ni-Al 2O3 -OAm, with a Ni loading of 5% for more obvious observation of particle changes. As shown in FIG. 3, the Ni particles were calcined at 750deg.C (5deg.C/min) and then reduced at 500deg.C (5deg.C/min) under a 5% H 2/Ar atmosphere for 2 hours, designated as "5% -Ni-Al 2O3 -OAm-750", and were found to be only 6.8nm by statistics, and EDS also demonstrated that Ni was well dispersed and no significant agglomeration occurred. This shows that the catalyst prepared by the method has better high-temperature resistant agglomeration performance and can be applied to some applications of high-temperature caused particle agglomeration and reaction deactivation.
Example 2
The embodiment provides a preparation method of a size-controllable high-dispersion ultra-small nanocluster, which comprises the following steps:
2g of Al 2O3 (19.62 mmol) and 5mL (15.48 mmol) of oleylamine were added to a flask containing 20mL of cyclohexane and 50mL of ethanol, and the mixture was subjected to ultrasonic dispersion for 30min, the solvents cyclohexane and ethanol were removed by using a rotary evaporator, and after sealing, the mixture was placed in a 100 ℃ oven to allow alumina to fully absorb oleylamine for 12h. The excess oil amine was removed by washing with 50mL of cyclohexane, centrifuging, drying, and placing 10.8mg of platinum acetylacetonate and pretreated alumina into a 50mL stainless steel ball mill tank containing 4 large stainless steel balls having a diameter of 20mm and 12 small stainless steel balls having a diameter of 10 mm. The ball milling pot was sealed and transferred to a three-dimensional high-speed vibratory ball mill (MSK-SFM-3), and the ball milling was run for 0.5h.
Then calcining at 500 ℃ for 2 hours at a heating rate of 5 ℃/min, and designating the prepared sample as 1% -Pt-Al 2O3 -OAm-500 according to the content, the adsorbent and the calcining temperature.
TEM and EDS of "1% -Pt-Al 2O3 -OAm-500" are shown in FIG. 4, and it can be seen from FIG. 4 that the particles of Pt are surprisingly 1.41nm, and EDS demonstrates uniform dispersion of Pt on Al 2O3.
Example 3
The embodiment provides a preparation method of a size-controllable high-dispersion ultra-small nanocluster, which comprises the following steps:
2g of Al 2O3 (19.62 mmol) and 5mL (15.48 mmol) of oleylamine were added to a flask containing 20mL of cyclohexane and 50mL of ethanol, and the mixture was subjected to ultrasonic dispersion for 30min, the solvents cyclohexane and ethanol were removed by using a rotary evaporator, and after sealing, the mixture was placed in a 100 ℃ oven to allow alumina to fully absorb oleylamine for 12h. The excess oil amine was removed by washing with 50mL of cyclohexane, centrifuging, drying, and placing 20.6mg of copper acetylacetonate and pretreated alumina into a 50mL stainless steel ball mill tank containing 4 large stainless steel balls of 20mm diameter and 12 small stainless steel balls of 10mm diameter. The ball milling pot was sealed and transferred to a three-dimensional high-speed vibratory ball mill (MSK-SFM-3), and the ball milling was run for 0.5h.
Then calcining at 500 ℃ for 2 hours at a heating rate of 5 ℃/min, and designating the prepared sample as 1% -Cu-SiO 2 -OAm-500 according to the content, adsorbent and calcining temperature.
FIG. 5 is a TEM and EDS image of 1% -Cu-SiO 2 -OAm-500. According to the large amount of statistical data shown in FIG. 5, the average particle size of 1% -Cu-SiO 2 -OAm-500 was 2.3nm. This is because the interaction between SiO 2 and OAm is limited and only a small number of OAm molecules are adsorbed, resulting in CuNCs that is not as uniform in size as Ni and PtNCs. No metal aggregation was observed, as demonstrated by the Cu element energy spectrum shown in fig. 5.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The preparation method of the size-controllable high-dispersion ultra-small nanoclusters is characterized by comprising the following steps of:
(1) Adding a surface modifier and an oxide into a solvent for ultrasonic dispersion to obtain a dispersion liquid;
(2) Spin-evaporating the dispersion liquid to remove the solvent, and completely adsorbing the surface modifier and the oxide under the heating condition to obtain a spin-evaporated product;
(3) Washing the rotary steaming material, and sequentially centrifuging and drying to obtain a pretreatment oxide;
(4) And mixing the pretreated oxide with metal precursor salt, and then sequentially ball-milling and calcining to obtain the size-controllable high-dispersion ultra-small nanocluster.
2. The method for preparing the size-controllable high-dispersion ultra-small nanoclusters according to claim 1, wherein in the step (1), the surface modifier is one of oleylamine, oleic acid, sodium oleate, glycerin, polyethylene glycol, stearyl mercaptan, octadecene, and cetyltrimethylammonium bromide;
And/or the oxide is one of alumina, titanium dioxide, cerium dioxide, silicon dioxide, zirconium oxide, magnesium oxide, ferric oxide and zinc oxide;
And/or the solvent is cyclohexane and ethanol.
3. The method for preparing the size-controllable high-dispersion ultra-small nanoclusters according to claim 2, wherein the volume ratio of cyclohexane to ethanol is 0.3 to 0.5:1;
and/or the mol ratio of the oleylamine to the alumina is 0.5-0.9:1.
4. The method for preparing ultra-small nanoclusters of controllable size and high dispersion according to claim 1, wherein the surface modifier and the oxide are fully adsorbed at 70 to 100 ℃ in the step (2).
5. The method for preparing the size-controllable high-dispersion ultra-small nanoclusters according to claim 1, wherein in the step (3), cyclohexane is used for washing the spin-steamed material.
6. The method for preparing size-controllable highly-dispersed ultra-small nanoclusters according to claim 1, wherein in the step (4), the metal precursor salt is one or a combination of two of acetylacetonate and acetate;
and/or the molar ratio of the metal precursor salt to the oxide is 0.005-0.1:1;
And/or the ball milling time is 0.25-1 h;
and/or the calcining temperature is 350-800 ℃ and the calcining time is 1-4 h.
7. The method for preparing the size-controllable high-dispersion ultra-small nanoclusters according to claim 6, wherein the acetylacetonate includes platinum acetylacetonate, copper acetylacetonate, nickel acetylacetonate, palladium acetylacetonate, rubidium acetylacetonate, rhodium acetylacetonate, cerium acetylacetonate and lanthanum acetylacetonate;
and/or the ball mill adopted in the ball milling process is a planetary ball mill, a high-energy ball mill, a three-dimensional high-speed vibration ball mill or manual grinding.
8. The ultra-small nanocluster of controllable size and high dispersion obtained by the preparation method of any one of claims 1 to 7.
9. Use of size-controllable highly dispersed ultra-small nanoclusters according to claim 8 for the preparation of heterogeneous thermal, electrocatalyst, photocatalyst and adsorbent.
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