CN114643364A - Synthesis method of core-shell structure nanoparticles of nickel-cobalt composite metal oxide coated nanogold - Google Patents
Synthesis method of core-shell structure nanoparticles of nickel-cobalt composite metal oxide coated nanogold Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title claims description 7
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- 229910017709 Ni Co Inorganic materials 0.000 claims 3
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- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- 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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
Abstract
The invention discloses a method for synthesizing core-shell structure nano particles of nickel-cobalt composite metal oxide coated nano gold, which comprises the following steps: (1) synthesizing Au nano particles with the particle size; (2) ultrasonically dispersing Au nano particles in absolute ethyl alcohol; (3) and sequentially adding a nickel chloride ethanol solution, a cobalt chloride ethanol solution, hydrazine hydrate and a sodium hydroxide ethanol solution, heating, stirring, reacting, and then centrifugally cleaning to obtain the nickel-cobalt composite metal oxide coated nanogold core-shell structure nanoparticles. According to the invention, the thickness of the shell layer of the nickel-cobalt composite oxide can be adjusted by changing the addition of the raw material of the nickel-cobalt salt, and the synthesized core-shell structure nano particle overcomes the limitation that the traditional catalyst is directly used for Raman detection and can not obtain a Raman signal of a reaction intermediate; by utilizing the Raman enhancement capability of the Au nanoparticles, an intermediate species signal in the surface reaction process of the catalyst shell layer can be obtained, and the research and application field of SERS is effectively widened.
Description
Technical Field
The invention belongs to the technical field of nanoparticle preparation, and particularly relates to a method for synthesizing core-shell structure nanoparticles of nickel-cobalt composite metal oxide coated nanogold.
Background
With the increasing consumption of traditional fossil energy such as coal, petroleum, natural gas and the like, the energy crisis and the environmental pollution problem become more serious. The search for efficient, clean and renewable energy sources (such as solar energy, wind energy, hydroelectric power, etc.) is becoming important. However, due to the inherent intermittent, fluctuating, and random nature of these renewable energy sources, it is difficult to connect to a normal power grid. Hydrogen energy is considered to be a clean secondary energy carrier and a good energy storage medium, and plays an increasingly important role. At present, a plurality of hydrogen production modes exist, but the hydrogen production modes face a plurality of difficulties, for example, the hydrogen production by alcohols can generate byproducts such as carbon monoxide and carbon dioxide, and the hydrogen production by biomass is unstable. The hydrogen production by water electrolysis is a key technology with rapid development, and has the advantages of high efficiency, high purity, small pollution and the like.
The electrolyzed water takes water as a raw material, a proper electrochemical system is built, electric energy is taken as an energy source, and the raw material water is respectively decomposed into hydrogen and oxygen at a cathode and an anode through an electrocatalyst. Water electrolysis involves two half-reactions, namely the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER). The OER reaction has a higher thermodynamic energy barrier (theoretical potential 1.23V) than HER, and requires a complex process that undergoes a transfer process of four electrons and formation of an O — O bond. OER is the rate-determining step of the overall water electrolysis process. Therefore, the selection of proper catalyst reduces the overpotential of OER reaction, and the improvement of kinetic performance is very important. The traditional OER catalyst mainly comprises Ru base, Ir base and the like, but is limited by low natural reserves, high price and the like, and the noble metal material cannot be commercialized in a large range. On the contrary, the transition metal oxides mainly containing Fe, Co and Ni have the characteristics of low cost, stability, small pollution and the like, are widely noticed by people, and are ideal substitutes of noble metal catalysts. Some studies have shown that the formation of transition bimetallic oxides by introducing other transition metal atoms with similar electronic configurations into transition monometallic oxides can significantly improve electrocatalytic activity.
With the continuous research of transition metal oxide OER catalysts, the catalytic activity is continuously improved. However, the reaction mechanism of the catalyst is still not fully understood. The research of the reaction mechanism has instructive significance for the construction and design of the catalyst. Even though many scholars report that intermediate species of the OER reaction are detected by using in-situ infrared, in-situ Raman and other technologies in sequence and give possible OER reaction mechanisms, many differences among different reported works are still unexplained, and the understanding of the mechanisms is still fuzzy.
Raman spectroscopy has been widely used as a surface sensitive vibrational spectrum. The method has the advantages of capability of detecting low wave number, no interference of water, no damage to samples and the like, and has deep application in the aspect of researching surface interface reaction mechanism. However, conventional raman spectroscopy is very sensitive and is not sufficient to detect most short-lived, weakly adsorbed reactive intermediate species. However, early scholars report that some precious metals represented by rough gold, silver and copper in nanometer level have the function of enhancing Raman spectrum signals. By constructing the core-shell structure nano particles of the noble metal @ catalyst, the catalyst has very strong Raman enhancement capability while catalyzing the reaction, can realize in-situ Raman detection in the reaction process, and has the advantages of high sensitivity, high reproducibility, simple and convenient operation and the like.
Therefore, constructing "core-shell structured" nanoparticles by coating the OER catalyst on the SERS enhancing substrate, such as gold nanoparticles, is a potential method for studying the OER reaction process.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for synthesizing nano-gold core-shell structure nanoparticles coated with nickel-cobalt composite metal oxide. In order to achieve the above purpose, one of the technical solutions of the present invention is: a method for synthesizing core-shell structured nanoparticles of nickel-cobalt composite metal oxide coated nanogold specifically comprises the following steps:
(1) synthesizing Au nano particles with the particle size of 50-60nm by adopting a sodium citrate method;
(2) taking out the Au nano particles prepared in the step (1), centrifuging to remove supernatant, and then ultrasonically dispersing in absolute ethyl alcohol;
(3) and sequentially adding a nickel chloride ethanol solution, a cobalt chloride ethanol solution, hydrazine hydrate and a sodium hydroxide ethanol solution into the Au sol dispersed by the ethanol, stirring and reacting for 10-20min under the heating condition of 40-60 ℃, and centrifugally cleaning to obtain the core-shell structure nano-particles of the nickel-cobalt composite metal oxide coated nano-gold.
In a preferred embodiment of the present invention, the method for synthesizing Au nanoparticles in step (1) is as follows: 2.425mL of chloroauric acid tetrahydrate solution with the mass fraction of 1% is dispersed in 200mL of ultrapure water, heating, stirring and condensation are started, and 1.5mL of 1% sodium citrate solution prepared in advance is added when the solution starts to boil, so that the Au nano particles with the particle size of 50-60nm can be obtained.
In a preferred embodiment of the present invention, in the step (2), 35-45mL of Au nanoparticles are taken, centrifuged to remove the supernatant, and then ultrasonically dispersed in 3-8mL of absolute ethanol, that is, the volume ratio of the Au nanoparticles to the absolute ethanol before centrifugation is 35-45: 3-8.
In a preferred embodiment of the present invention, in the step (3), the volume ratio of the nickel chloride ethanol solution, the cobalt chloride ethanol solution, the hydrazine hydrate and the sodium hydroxide ethanol solution is 0.6-2mL:1.2-4mL:50-70 μ L:1mL, the concentration of the nickel chloride ethanol solution is 1mM, the concentration of the cobalt chloride ethanol solution is 1mM, and the concentration of the sodium hydroxide ethanol solution is 0.5M.
In a preferred embodiment of the invention, in the step (3), the reaction device is placed in a water bath at 40-60 ℃ for heating for 10-20min, but the particles are easy to agglomerate and are taken out when not needed, and the dispersibility is improved by ultrasound.
The second technical scheme of the invention is as follows: the core-shell structure nano particle prepared by the synthesis method of the nickel-cobalt composite metal oxide coated nano gold core-shell structure nano particle has a core-shell structure, gold is used as a core, the nickel-cobalt composite metal oxide is used as a shell, the molar ratio of the gold to the nickel-cobalt composite metal oxide is 1.4-1.8:1, the molar ratio of the nickel metal oxide to the cobalt metal oxide in the nickel-cobalt composite metal oxide is 1-3.3:2-6.7, the particle size range of the gold particle is 50-60nm, and the thickness range of the shell layer is 1-11 nm.
The third technical scheme of the invention is as follows: an application of core-shell structured nanoparticles of nickel-cobalt composite metal oxide coated nanogold in an in-situ Raman three-electrode system specifically comprises the following steps: dropping the concentrated core-shell structured nano-particles of the nickel-cobalt composite metal oxide coated nano-gold on a glassy carbon electrode to be used as a working electrode, drying and assembling the nano-particles in a three-electrode system suitable for in-situ Raman, wherein the electrolyte is 1M potassium hydroxide solution; and testing the electrocatalytic reaction process of the core-shell structure nano particles under different potentials by applying different potentials and in-situ Raman spectroscopy.
In a preferred embodiment of the present invention, the concentrated ni — co complex metal oxide-coated nanogold core-shell structure nanoparticles are fully ultrasonically treated to ensure that the nanoparticles are fully dispersed, so that a layer of nanoparticles can be uniformly dispersed on the electrode, and the nanoparticles are not completely agglomerated.
In a preferred embodiment of the present invention, since the electrolyte in the three-electrode system is a strong alkaline solution, the reference electrode can be selected from a mercury/mercury oxide electrode, a silver/silver chloride electrode, and the like.
In a preferred embodiment of the present invention, in the in-situ raman spectroscopy testing process, it is ensured that after the potential is changed each time, the raman testing is performed after the electrode state is stabilized by waiting for more than 30 seconds. And in the in-situ test process, the consistency of parameters and the stability of the device are ensured.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a nickel-cobalt composite metal oxide coated nanogold core-shell structure nanoparticle which can be used for in-situ Raman spectrum research, wherein a nickel-cobalt composite metal oxide shell layer is used as a catalyst and is an active site of an electrochemical OER reaction. The kernel gold is used as a Raman signal amplifier, can monitor the Raman signal of the intermediate species adsorbed on the surface of the nickel-cobalt composite metal oxide shell in real time and in situ and reflect the Raman signal on a spectrum, and can deduce the reaction mechanism of the catalysis of the oxide shell by correspondingly applying potential to analyze a spectrum peak and combining theoretical calculation. The structure has the advantages of integrity and functionality of the structure, has dual functions of catalytic activity and mechanism representation, can be used for analyzing the reaction mechanism of the high-efficiency OER catalyst, namely nickel-cobalt oxide, and has the advantages of simplicity, convenience, high reproducibility, high Raman sensitivity and the like.
2. The invention provides a synthesis method of 'core-shell structure' nano particles of nickel-cobalt composite metal oxide coated nano gold, which has the advantages of adjustable synthesis process and high reproducibility; the thickness of the nickel-cobalt composite metal oxide shell layer can be adjusted by changing the adding amount of the nickel salt and the cobalt salt.
3. The synthesized nano particles with the core-shell structure overcome the limitation that the traditional catalyst is directly used for Raman detection and can not obtain a Raman signal of a reaction intermediate; by utilizing the Raman enhancement capability of the Au nanoparticles, an intermediate species signal in the surface reaction process of the catalyst shell layer can be obtained, and the research and application field of SERS is effectively widened.
4. The synthesis method can be used as a reference method for constructing the core-shell structure nano particles by using oxides of nickel, cobalt, iron and manganese and multi-element metal oxides; the synthesis method is very convenient, and the synthesized particles can be stored for a long time after being dispersed in ethanol or water.
Drawings
FIG. 1 is a plot of the in situ Raman spectra of nanoparticles prepared in example 1; (ii) a
FIG. 2 is an electrochemical cyclic voltammogram of the nanoparticles prepared in example 1;
FIG. 3 is a transmission electron microscope photograph of nanoparticles prepared in examples 1-3,
wherein, fig. a is embodiment 1, fig. b is embodiment 2, and fig. c is embodiment 3.
Detailed Description
The invention is further explained below with reference to the figures and the specific embodiments.
(1) Synthesizing Au nano particles with the particle size of 50-60nm by adopting a sodium citrate method;
(2) taking out the Au nano particles prepared in the step (1), centrifuging to remove supernatant, and then ultrasonically dispersing in absolute ethyl alcohol;
(3) and sequentially adding a nickel chloride ethanol solution, a cobalt chloride ethanol solution, hydrazine hydrate and a sodium hydroxide ethanol solution into the Au sol dispersed by the ethanol, stirring and reacting for 10-20min under the heating condition of 40-60 ℃, and centrifugally cleaning to obtain the core-shell structure nano-particles of the nickel-cobalt composite metal oxide coated nano-gold.
Example 1
A core-shell structure nanoparticle with gold as core and nickel-cobalt composite metal oxide as shell, wherein the gold particle diameter is 55nm, and the shell thickness is 1-2 nm; the molar ratio of the gold to the nickel-cobalt metal oxide is 1.4-1.8:1, and the molar ratio of the nickel metal oxide to the cobalt metal oxide in the nickel-cobalt composite metal oxide is 1-3.3: 2-6.7. The preparation method comprises the following specific steps:
(1) synthesizing Au nano particles with the particle size of about 55nm by adopting a sodium citrate method, dispersing 2.425mL of 1% by mass fraction chloroauric acid solution in 200mL of ultrapure water, starting heating, stirring and condensing, and adding 1.5mL of 1% prepared sodium citrate solution when the solution starts to boil to obtain 55nm Au nano particle sol;
(2) taking 40mL of the Au nanoparticle sol, centrifuging to remove supernatant, and dispersing with 5mL of absolute ethyl alcohol;
(3) adding 0.6mL of 1mM nickel chloride ethanol solution, 1.2 mL of 1mM cobalt chloride ethanol solution, 60 mu L of hydrazine hydrate and 1mL of 0.5M sodium hydroxide ethanol solution into the Au nano particle sol dispersed by the absolute ethyl alcohol in sequence;
(4) and (3) reacting for 15min under the heating condition of 50 ℃, and centrifugally cleaning to obtain the core-shell structure nano-particles of the nickel-cobalt composite metal oxide coated nano-gold.
Fully ultrasonically dropping the core-shell structure nano particles on a glassy carbon electrode to be used as a working electrode, drying and assembling the core-shell structure nano particles in a three-electrode system suitable for in-situ Raman, wherein the counter electrode is a platinum wire, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is 1M potassium hydroxide solution; and (3) carrying out in-situ Raman spectrum testing by applying 8 different potentials between 0.90 and 1.55V, waiting for 40 seconds after changing the potential each time, and carrying out Raman testing after stabilizing the electrode state, wherein in the in-situ testing process, the parameters are consistent and the device is stable.
The in situ Raman spectra of the nanoparticles at different potentials are shown in FIG. 1. As can be seen from the electrochemical Raman spectrum of FIG. 1, the low potential is due to Ni (OH)2The scattering cross section of (a) is small, mainly showing the spectral peaks of CoOOH. With the increase of the potential, the OER active species Ni (III) -O and 800-1200cm-1The species of (2) appear. The latter has been demonstrated to be a superoxide species adsorbed on the nickel surface, an active intermediate in oxygen evolution reactions.
FIG. 2 is a graph of electrochemical cyclic voltammetry of the core-shell structured nanoparticle, and it can be seen from FIG. 2 that the redox pair peaks of Ni (II) and Ni (III) are consistent with the potential appearing in the Raman spectrogram of Ni (III) -O, and it is proved that trivalent nickel is used as a site to adsorb active oxygen species, so as to initiate the subsequent oxygen evolution reaction, and the initial overpotential of the oxygen evolution reaction is 320mV, which has excellent catalytic performance.
Example 2
A core-shell structure nanoparticle with gold as core and nickel-cobalt composite metal oxide as shell, wherein the gold particle diameter is 55nm, and the shell thickness is 3-4 nm; the molar ratio of the gold to the nickel-cobalt metal oxide is 1.4-1.8:1.7, and the molar ratio of the nickel metal oxide to the cobalt metal oxide in the nickel-cobalt composite metal oxide is 1-3.3: 2-6.7. The preparation method of the nickel-cobalt composite metal oxide coated nanogold core-shell structure nano particle is the same as that in example 1, except that the addition amounts of a nickel chloride ethanol solution and a cobalt chloride ethanol solution are respectively 1mL and 2 mL.
Example 3
A nickel-cobalt composite metal oxide coated nano gold core-shell structured nano particle, gold is a core, nickel-cobalt composite metal oxide is a shell, the particle size of the gold particle is 55nm, and the thickness of the shell layer is 9-11 nm; the specific preparation method is the same as example 1 except that the addition amounts of the nickel chloride ethanol solution and the cobalt chloride ethanol solution are respectively 2mL and 4 mL.
The transmission electron microscope images of the core-shell structure nanoparticles prepared by adding different amounts of the ethanol solutions of nickel chloride and cobalt chloride to the solutions of examples 1 to 3 are shown in fig. 3, and it can be seen from fig. 3 that the shell thickness gradually increases with the addition of the ethanol solutions of nickel chloride and cobalt chloride. It follows that the thickness of the nickel cobalt oxide shell layer can be adjusted by adjusting the amounts of nickel salt and cobalt salt.
The above embodiments are merely preferred embodiments of the present invention, which are provided for illustrating the principles and effects of the present invention and not for limiting the present invention. It should be noted that modifications to the above-described embodiments can be made by persons skilled in the art without departing from the spirit and scope of the present invention and such modifications should also be considered as within the scope of the present invention.
Claims (10)
1. A method for synthesizing nano particles with a core-shell structure of nickel-cobalt composite metal oxide coated with nano gold is characterized by comprising the following steps:
(1) synthesizing Au nano particles;
(2) centrifuging the Au nanoparticles, and ultrasonically dispersing the Au nanoparticles in absolute ethyl alcohol;
(3) and sequentially adding a nickel chloride ethanol solution, a cobalt chloride ethanol solution, hydrazine hydrate and a sodium hydroxide ethanol solution into the Au sol dispersed by the absolute ethanol, heating, stirring, reacting, and centrifugally cleaning to obtain the nickel-cobalt composite metal oxide coated nanogold core-shell structure nano particles.
2. The method for synthesizing nanoparticles with core-shell structure of ni-co complex metal oxide coated with nanogold according to claim 1, wherein the method for synthesizing Au nanoparticles in step (1) comprises the steps of taking 2.425mL of chloroauric acid tetrahydrate solution with mass fraction of 1% to disperse in 200mL of ultrapure water, starting heating, stirring and condensing, and adding 1.5mL of 1% sodium citrate solution prepared in advance when the solution starts to boil, thereby obtaining Au nanoparticles with a particle size of 50-60 nm.
3. The method for synthesizing nanoparticles with core-shell structure of Ni-Co composite metal oxide coated with nano-Au according to claim 1, wherein the volume ratio of Au nanoparticles to absolute ethyl alcohol before centrifugation in step (2) is 35-45: 3-8.
4. The method for synthesizing nanoparticles with core-shell structure of Ni-Co composite metal oxide coated with nano-Au according to claim 1, wherein the volume ratio of the ethanol solution of nickel chloride, the ethanol solution of cobalt chloride, hydrazine hydrate and the ethanol solution of sodium hydroxide in the step (3) is 0.6-2mL:1.2-4mL:50-70 μ L:1mL, the concentration of the ethanol solution of nickel chloride is 1mM, the concentration of the ethanol solution of cobalt chloride is 1mM, and the concentration of the ethanol solution of sodium hydroxide is 0.5M.
5. The method for synthesizing nanoparticles with core-shell structure of Ni-Co composite metal oxide coated with nano-Au according to claim 1, wherein the heating temperature in step (3) is 40-60 ℃ and the heating time is 10-20 min.
6. A core-shell structured nanoparticle of NiCo complex metal oxide coated Nanogold prepared by the synthesis method according to any one of claims 1 to 5, wherein the nanoparticle has a core-shell structure, gold is the core, NiCo complex metal oxide is the shell, and the molar ratio of gold to NiCo complex metal oxide is 1.4-1.8: 1-3. The molar ratio of nickel metal oxide to cobalt metal oxide in the nickel-cobalt composite metal oxide is 1-3.3:2-6.7, the particle size range of the gold particles is 50-60nm, and the thickness range of the shell layer is 1-11 nm.
7. An application of a core-shell structure nano particle of nickel-cobalt composite metal oxide coated with nano gold in an in-situ Raman three-electrode system.
8. The application of the nickel-cobalt composite metal oxide coated nanogold core-shell structure nanoparticle in an in-situ Raman three-electrode system according to claim 6 is characterized by specifically comprising the following steps: dropping the concentrated core-shell structure nano-particles of the nickel-cobalt composite metal oxide coated nano-gold on a glassy carbon electrode to be used as a working electrode, drying and assembling the nano-particles in a three-electrode system suitable for in-situ Raman, wherein the electrolyte is 1M potassium hydroxide solution; and testing the electrocatalytic reaction process of the core-shell structure nano particles under different potentials by applying different potentials through the in-situ Raman spectroscopy.
9. The use of the ni-co composite metal oxide coated nanogold core-shell nanoparticle in an in-situ raman three-electrode system according to claim 8, wherein the concentrated ni-co composite metal oxide coated nanogold core-shell nanoparticle requires ultrasonic dispersion.
10. The use of the ni-co complex metal oxide coated nanogold core-shell structured nanoparticle according to any one of claim 8 in an in-situ raman three-electrode system, wherein a reference electrode in the three-electrode system is one of a mercury/mercury oxide electrode and a silver/silver chloride electrode, the in-situ raman spectroscopy test process is performed after the potential is changed for more than 30 seconds, and the raman test is performed after the electrode state is stable.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115188976A (en) * | 2022-06-24 | 2022-10-14 | 国联汽车动力电池研究院有限责任公司 | Zinc-air battery cathode catalyst and preparation method thereof |
| CN115739109A (en) * | 2022-09-02 | 2023-03-07 | 厦门大学 | Preparation method of AuCu catalyst with Raman enhancement capability and satellite structure |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101263A (en) * | 2007-07-20 | 2008-01-09 | 苏州大学 | Core-shell nano granule with high activity surface intensified raman spectrum and preparation method thereof |
| CN102969514A (en) * | 2012-12-03 | 2013-03-13 | 哈尔滨工业大学 | Metal-coated oxide nano core-shell structure catalyst and preparation method thereof |
| JP2015030882A (en) * | 2013-08-02 | 2015-02-16 | 株式会社ノリタケカンパニーリミテド | Base metal - noble metal composite nanoparticles and method for producing the same |
| CN108579758A (en) * | 2018-03-23 | 2018-09-28 | 中国科学院宁波材料技术与工程研究所 | A kind of controllable bimetallic nanometer nuclear shell nano-structure, catalyst, its preparation method and application |
| CN109926578A (en) * | 2019-02-26 | 2019-06-25 | 中国科学院化学研究所 | A kind of surface enhanced Raman scattering substrate material, preparation method and application |
| US20190247918A1 (en) * | 2016-10-26 | 2019-08-15 | Council Of Scientific And Industrial Research | An improved process for the preparation of bimetallic core-shell nanoparticles and their catalytic applications |
| CN111987318A (en) * | 2020-09-28 | 2020-11-24 | 海南尚合超电新能源科技有限公司 | Preparation method of nickel-cobalt-based oxide coated ternary lithium ion positive electrode material |
-
2022
- 2022-03-01 CN CN202210197496.0A patent/CN114643364A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101263A (en) * | 2007-07-20 | 2008-01-09 | 苏州大学 | Core-shell nano granule with high activity surface intensified raman spectrum and preparation method thereof |
| CN102969514A (en) * | 2012-12-03 | 2013-03-13 | 哈尔滨工业大学 | Metal-coated oxide nano core-shell structure catalyst and preparation method thereof |
| JP2015030882A (en) * | 2013-08-02 | 2015-02-16 | 株式会社ノリタケカンパニーリミテド | Base metal - noble metal composite nanoparticles and method for producing the same |
| US20190247918A1 (en) * | 2016-10-26 | 2019-08-15 | Council Of Scientific And Industrial Research | An improved process for the preparation of bimetallic core-shell nanoparticles and their catalytic applications |
| CN108579758A (en) * | 2018-03-23 | 2018-09-28 | 中国科学院宁波材料技术与工程研究所 | A kind of controllable bimetallic nanometer nuclear shell nano-structure, catalyst, its preparation method and application |
| CN109926578A (en) * | 2019-02-26 | 2019-06-25 | 中国科学院化学研究所 | A kind of surface enhanced Raman scattering substrate material, preparation method and application |
| CN111987318A (en) * | 2020-09-28 | 2020-11-24 | 海南尚合超电新能源科技有限公司 | Preparation method of nickel-cobalt-based oxide coated ternary lithium ion positive electrode material |
Non-Patent Citations (1)
| Title |
|---|
| LILI WANG，ETALS: "Rattle-type Au@NiCo LDH hollow core-shell nanostructures for nonenzymatic glucose sensing", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115188976A (en) * | 2022-06-24 | 2022-10-14 | 国联汽车动力电池研究院有限责任公司 | Zinc-air battery cathode catalyst and preparation method thereof |
| CN115739109A (en) * | 2022-09-02 | 2023-03-07 | 厦门大学 | Preparation method of AuCu catalyst with Raman enhancement capability and satellite structure |
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