CN110127749B - A kind of preparation method of cuprous sulfide nanoflowers containing copper defects - Google Patents
A kind of preparation method of cuprous sulfide nanoflowers containing copper defects Download PDFInfo
- Publication number
- CN110127749B CN110127749B CN201910450346.4A CN201910450346A CN110127749B CN 110127749 B CN110127749 B CN 110127749B CN 201910450346 A CN201910450346 A CN 201910450346A CN 110127749 B CN110127749 B CN 110127749B
- Authority
- CN
- China
- Prior art keywords
- cuprous sulfide
- water
- mass ratio
- nanoflower
- copper
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Catalysts (AREA)
- Hybrid Cells (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及一种含铜缺陷的硫化亚铜纳米花的制备方法，属于纳米材料技术领域。本发明将强碱、表面活性剂、单质铜、水合肼、硫化钠与水混合均匀，在密封条件下匀速升温至温度为180~220℃并恒温反应22~24 h得到反应体系；反应体系冷却至室温，离心分离，去除上层清液，再采用去离子水洗涤至洗涤液为中性，干燥即得硫化亚铜纳米花。本发明方法反应条件温和、产率高、产物形貌比较均匀而且重复性好，制得的硫化亚铜纳米花的平均粒径为700 nm~1.9μm，组成纳米花的纳米片的平均粒径为400 nm左右；本发明硫化亚铜纳米花具有分级结构和含铜缺陷，可应用在光催化剂、太阳能电池、电化学储能器件和传感器等领域。The invention relates to a preparation method of cuprous sulfide nanoflowers containing copper defects, belonging to the technical field of nanomaterials. In the present invention, strong base, surfactant, elemental copper, hydrazine hydrate, sodium sulfide and water are mixed uniformly, and the temperature is uniformly heated to 180-220° C. under sealing conditions, and a reaction system is obtained by constant temperature reaction for 22-24 h; the reaction system is cooled down After reaching room temperature, centrifuging, removing the supernatant, washing with deionized water until the washing liquid is neutral, and drying to obtain cuprous sulfide nanoflowers. The method of the invention has mild reaction conditions, high yield, relatively uniform product morphology and good repeatability. It is about 400 nm; the cuprous sulfide nanoflowers of the invention have a hierarchical structure and copper-containing defects, and can be applied in the fields of photocatalysts, solar cells, electrochemical energy storage devices, sensors and the like.
Description
Technical Field
The invention relates to a preparation method of cuprous sulfide nanoflower with copper defects, and belongs to the technical field of nanomaterials.
Background
The cuprous sulfide is low in price, is an important transition metal sulfide, and is a multifunctional semiconductor material with good chemical stability. The nano cuprous sulfide material has small particle size and large specific surface area, and has incomparable optical, electric and electrochemical properties compared with a block material due to quantum size effect, surface effect and macroscopic quantum tunnel effect, so the cuprous sulfide nano material is widely applied to the fields of photocatalysts, solar cells, electrochemical energy storage devices, sensors and the like, and is widely concerned and researched by people. The cuprous sulfide nano material can be prepared by a plurality of methods, such as a chemical precipitation method, a microwave radiation method, a vapor deposition method, an in-phase method, a sol-gel method, a microemulsion method, a hydrothermal synthesis method, a spray pyrolysis method, an ultrasonic synthesis method and the like. These methods have some disadvantages, such as difficult control of the size or morphology of the product, low yield, harsh reaction conditions, complex preparation process, and relatively high cost.
Disclosure of Invention
The method for preparing the cuprous sulfide nanoflower with the copper defect and the hierarchical structure is characterized by mild reaction conditions, simple operation and high yield, and the prepared cuprous sulfide nanoflower has the characteristics of controllable size, regular shape and the like.
A preparation method of cuprous sulfide nanoflower containing copper defects comprises the following specific steps:
mixing strong base, a surfactant, elemental copper, hydrazine hydrate, sodium sulfide and water, uniformly mixing, uniformly heating to 180-220 ℃ under a sealed condition at a constant speed, and reacting at a constant temperature for 22-24 hours to obtain a reaction system; and cooling the reaction system to room temperature, performing centrifugal separation, removing supernatant, washing with absolute ethyl alcohol and deionized water until the washing liquid is neutral, and drying to obtain the cuprous sulfide nanoflower.
The strong base is a composite base of potassium hydroxide and sodium hydroxide.
Further, the mass ratio of the potassium hydroxide to the sodium hydroxide is within the range of 2 (1-2).
The surfactant is trimethyl hexadecyl ammonium bromide.
The mass ratio of the strong base to the water is 10 (1-5), the mass ratio of the surfactant to the water is 0.72 (1-5), the mass ratio of the elemental copper to the sodium sulfide is 2 (1-15), the mass ratio of the elemental copper to the water is 0.4 (1-5), and the volume ratio of the hydrazine hydrate to the water is 0.05 (1-5).
The addition amount of the deionized water is based on the full reaction of simple substance copper and salt energy, a powder product cannot be obtained without adding water, the more the product is added, but the excessive water is added, the product has a particle-like or uneven appearance;
the sealing is to prevent evaporation of moisture to ensure more complete reaction and to improve yield.
Preferably, the drying temperature is 30-80 ℃; the yield, the product morphology and the stability of the product can be ensured;
preferably, the elemental copper is copper.
The average particle size of the cuprous sulfide nanoflower is 700 nm-1.9 mu m, and the average particle size of nanosheets forming the nanoflower is 350-600 nm;
the molecular formula of the cuprous sulfide nanoflower is Cu7.2S4；
The invention has the beneficial effects that:
(1) the method takes strong base, surfactant, elemental copper, hydrazine hydrate, salt and water as raw materials to prepare the cuprous sulfide nanoflower under mild conditions, and the process has the advantages of low synthesis temperature, low pressure, high yield, regular product morphology and good repeatability;
(2) the cuprous sulfide nanoflower has a hierarchical structure and copper-containing defects, and can be applied to the fields of photocatalysts, solar cells, electrochemical energy storage devices, sensors and the like;
(3) the method disclosed by the invention is simple to operate, the preparation process is easy to control, the method is suitable for industrial production, and the method is low in production cost and environment-friendly.
Drawings
FIG. 1 is an X-ray diffraction pattern of the cuprous sulfide nanoflower of example 1;
FIG. 2 is a scanning electron micrograph of the cuprous sulfide nanoflower of example 1;
FIG. 3 is a scanning electron micrograph of the cuprous sulfide nanoflower of example 2;
FIG. 4 is a scanning electron micrograph of the cuprous sulfide nanoflower of example 3;
FIG. 5 is a scanning electron micrograph of the cuprous sulfide nanoflower of example 4;
FIG. 6 is a scanning electron micrograph of cuprous sulfide nanoflower of example 5;
FIG. 7 is a scanning electron micrograph of cuprous sulfide nanoflower of example 6;
FIG. 8 is a scanning electron micrograph of cuprous sulfide nanoflower of example 7.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a preparation method of cuprous sulfide nanoflower containing copper defects comprises the following specific steps:
uniformly mixing strong base (composite alkali of potassium hydroxide and sodium hydroxide), surfactant (trimethyl hexadecyl ammonium bromide CTAB), elemental copper (copper sheet), hydrazine hydrate, sodium sulfide nonahydrate and deionized water, sealing in a polytetrafluoroethylene container, placing the polytetrafluoroethylene container in heating equipment, heating at a constant speed to 200 ℃ and reacting at a constant temperature for 24 hours, cooling to room temperature, performing centrifugal separation, removing supernatant, washing with absolute ethyl alcohol and deionized water until the washing liquid is neutral, and drying at 30 ℃ to obtain cuprous sulfide nanoflowers; wherein the mass ratio of potassium hydroxide to sodium hydroxide is 5.65:4.35, the mass ratio of strong base (composite base of potassium hydroxide and sodium hydroxide) to water is 10:1, the mass ratio of surfactant (trimethyl cetyl ammonium bromide CTAB) to water is 0.72:1, the mass ratio of elemental copper to sodium sulfide is 2:1, the mass ratio of elemental copper to water is 0.4:1, and the volume ratio of hydrazine hydrate to water is 0.05: 1;
the X-ray diffraction pattern of the cuprous sulfide nanoflower is shown in figure 1, and as can be seen from figure 1, the product has good crystallinity, and the product and Cu are mixed7.2S4PDF #24-0061 card match, indicating that the resulting product is cuprous sulfide Cu with copper defects7.2S4In addition, the half-peak width of the width reflects the thin thickness of the nanosheets forming the nanoflower, which is consistent with a scanning electron microscope picture;
as shown in fig. 2, a scanning electron microscope image of the cuprous sulfide nanoflower in this embodiment shows that the sample is a nanoflower composed of nanosheets, the average particle size of the nanoflower is about 800 nm, the average particle size of the nanosheets composing the nanoflower is about 400 nm, and the overall morphology is uniform.
Example 2: a preparation method of cuprous sulfide nanoflower containing copper defects comprises the following specific steps:
uniformly mixing strong base (composite alkali of potassium hydroxide and sodium hydroxide), surfactant (trimethyl hexadecyl ammonium bromide CTAB), elemental copper (copper sheet), hydrazine hydrate, sodium sulfide nonahydrate and deionized water, sealing in a polytetrafluoroethylene container, placing the polytetrafluoroethylene container in heating equipment, heating at a constant speed to 200 ℃ and reacting at a constant temperature for 24 hours, cooling to room temperature, performing centrifugal separation, removing supernatant, washing with absolute ethyl alcohol and deionized water until the washing liquid is neutral, and drying at 40 ℃ to obtain cuprous sulfide nanoflower; wherein the mass ratio of potassium hydroxide to sodium hydroxide is 5.65:4.35, the mass ratio of strong base (composite base of potassium hydroxide and sodium hydroxide) to water is 10:3, the mass ratio of surfactant (trimethyl cetyl ammonium bromide CTAB) to water is 0.72:3, the mass ratio of elemental copper to sodium sulfide is 2:1, the mass ratio of elemental copper to water is 0.4:3, and the volume ratio of hydrazine hydrate to water is 0.05: 3;
as shown in fig. 3, a scanning electron microscope image of the cuprous sulfide nanoflower in this embodiment shows that, as shown in fig. 3, the sample is a nanoflower composed of nanosheets, the average particle size of the nanoflower is about 1.2 μm, the average particle size of the nanosheets composing the nanoflower is about 600nm, and the overall appearance is uniform.
Example 3: a preparation method of cuprous sulfide nanoflower containing copper defects comprises the following specific steps:
uniformly mixing strong base (composite alkali of potassium hydroxide and sodium hydroxide), surfactant (trimethyl hexadecyl ammonium bromide CTAB), elemental copper (copper sheet), hydrazine hydrate, sodium sulfide nonahydrate and deionized water, sealing in a polytetrafluoroethylene container, placing the polytetrafluoroethylene container in heating equipment, heating at a constant speed to 200 ℃ and reacting at a constant temperature for 24 hours, cooling to room temperature, performing centrifugal separation, removing supernatant, washing with absolute ethyl alcohol and deionized water until the washing liquid is neutral, and drying at 50 ℃ to obtain cuprous sulfide nanoflower; wherein the mass ratio of potassium hydroxide to sodium hydroxide is 2:1, the mass ratio of strong base (composite base of potassium hydroxide and sodium hydroxide) to water is 2:1, the mass ratio of surfactant (trimethyl cetyl ammonium bromide CTAB) to water is 0.72:5, the mass ratio of elemental copper to sodium sulfide is 2:1, the mass ratio of elemental copper to water is 0.4:5, and the volume ratio of hydrazine hydrate to water is 0.05: 5;
as shown in fig. 4, a scanning electron microscope image of the cuprous sulfide nanoflower in this embodiment shows that, as shown in fig. 4, the sample is a nanoflower composed of nanosheets, the average particle size of the nanoflower is about 900 nm, the average particle size of the nanosheets composing the nanoflower is about 450 nm, and the overall morphology is relatively uniform.
Example 4: a preparation method of cuprous sulfide nanoflower containing copper defects comprises the following specific steps:
uniformly mixing strong base (composite alkali of potassium hydroxide and sodium hydroxide), surfactant (trimethyl hexadecyl ammonium bromide CTAB), elemental copper (copper sheet), hydrazine hydrate, sodium sulfide nonahydrate and deionized water, sealing in a polytetrafluoroethylene container, placing the polytetrafluoroethylene container in heating equipment, heating at a constant speed to 200 ℃ and reacting at a constant temperature for 24 hours, cooling to room temperature, performing centrifugal separation, removing supernatant, washing with absolute ethyl alcohol and deionized water until the washing liquid is neutral, and drying at 60 ℃ to obtain cuprous sulfide nanoflower; wherein the mass ratio of potassium hydroxide to sodium hydroxide is 1:1, the mass ratio of strong base (composite base of potassium hydroxide and sodium hydroxide) to water is 10:1, the mass ratio of surfactant (trimethyl cetyl ammonium bromide CTAB) to water is 0.72:1, the mass ratio of elemental copper to sodium sulfide is 2:15, the mass ratio of elemental copper to water is 0.4:1, and the volume ratio of hydrazine hydrate to water is 0.05: 1;
as shown in fig. 5, a scanning electron microscope image of the cuprous sulfide nanoflower in this embodiment shows that, as shown in fig. 5, the sample is a nanoflower composed of nanosheets, the average particle size of the nanoflower is about 700 nm, the average particle size of the nanosheets composing the nanoflower is about 350 nm, and the overall morphology is relatively uniform.
Example 5: a preparation method of cuprous sulfide nanoflower containing copper defects comprises the following specific steps:
uniformly mixing strong base (composite alkali of potassium hydroxide and sodium hydroxide), surfactant (trimethyl hexadecyl ammonium bromide CTAB), elemental copper (copper sheet), hydrazine hydrate, sodium sulfide nonahydrate and deionized water, sealing in a polytetrafluoroethylene container, placing the polytetrafluoroethylene container in heating equipment, heating at a constant speed to 200 ℃, reacting at a constant temperature for 20 hours, cooling to room temperature, performing centrifugal separation, removing supernatant, washing with absolute ethyl alcohol and deionized water until the washing solution is neutral, and drying at 80 ℃ to obtain cuprous sulfide nanoflower; wherein the mass ratio of potassium hydroxide to sodium hydroxide is 2:1.3, the mass ratio of strong base (composite alkali of potassium hydroxide and sodium hydroxide) to water is 10:1, the mass ratio of surfactant (trimethyl cetyl ammonium bromide CTAB) to water is 0.72:1, the mass ratio of elemental copper to sodium sulfide is 1:1, the mass ratio of elemental copper to water is 0.4:1, and the volume ratio of hydrazine hydrate to water is 0.05: 1;
the scanning electron microscope image of the cuprous sulfide nanoflower in this example is shown in fig. 6, and as can be seen from fig. 6, the average particle size of the cuprous sulfide nanoflower in this example is about 1.5 μm, and the overall morphology is relatively uniform.
Example 6: a preparation method of cuprous sulfide nanoflower containing copper defects comprises the following specific steps:
uniformly mixing strong base (composite alkali of potassium hydroxide and sodium hydroxide), surfactant (trimethyl hexadecyl ammonium bromide CTAB), elemental copper (copper sheet), hydrazine hydrate, sodium sulfide nonahydrate and deionized water, sealing in a polytetrafluoroethylene container, placing the polytetrafluoroethylene container in heating equipment, heating at a constant speed to 190 ℃, reacting at a constant temperature for 24 hours, cooling to room temperature, performing centrifugal separation, removing supernatant, washing with absolute ethyl alcohol and deionized water until the washing solution is neutral, and drying at the temperature of 30 ℃ to obtain cuprous sulfide nanoflower; wherein the mass ratio of potassium hydroxide to sodium hydroxide is 2:1.6, the mass ratio of strong base (composite alkali of potassium hydroxide and sodium hydroxide) to water is 5:1, the mass ratio of surfactant (trimethyl cetyl ammonium bromide CTAB) to water is 0.72:2, the mass ratio of elemental copper to sodium sulfide is 2:7, the mass ratio of elemental copper to water is 0.2:1, and the volume ratio of hydrazine hydrate to water is 0.05: 2;
the scanning electron micrograph of the cuprous sulfide nanoflower in the embodiment is shown in fig. 7, and as can be seen from fig. 7, the average particle size of the cuprous sulfide nanoflower in the embodiment is about 1.7 μm, and the overall morphology is relatively uniform.
Example 7: a preparation method of cuprous sulfide nanoflower containing copper defects comprises the following specific steps:
uniformly mixing strong base (composite alkali of potassium hydroxide and sodium hydroxide), surfactant (trimethyl hexadecyl ammonium bromide CTAB), elemental copper (copper sheet), hydrazine hydrate, sodium sulfide nonahydrate and deionized water, sealing in a polytetrafluoroethylene container, placing the polytetrafluoroethylene container in heating equipment, heating at a constant speed to 220 ℃ and reacting at a constant temperature for 22 hours, cooling to room temperature, performing centrifugal separation, removing supernatant, washing with absolute ethyl alcohol and deionized water until the washing liquid is neutral, and drying at 50 ℃ to obtain cuprous sulfide nanoflower; wherein the mass ratio of potassium hydroxide to sodium hydroxide is 1:1, the mass ratio of strong base (composite base of potassium hydroxide and sodium hydroxide) to water is 10:1, the mass ratio of surfactant (trimethyl cetyl ammonium bromide CTAB) to water is 0.72:1, the mass ratio of elemental copper to sodium sulfide is 2:15, the mass ratio of elemental copper to water is 0.4:1, and the volume ratio of hydrazine hydrate to water is 0.05: 1;
the scanning electron microscope image of the cuprous sulfide nanoflower in the embodiment is shown in fig. 8, and as can be seen from fig. 8, the average particle size of the cuprous sulfide nanoflower in the embodiment is about 1.9 μm, and the overall morphology is relatively uniform.
Claims (4)
1. A preparation method of cuprous sulfide nanoflower containing copper defects is characterized by comprising the following specific steps:
uniformly mixing strong base, a surfactant, elemental copper, hydrazine hydrate, sodium sulfide and water, uniformly heating to 180-220 ℃ under a sealed condition, and reacting at a constant temperature for 22-24 hours to obtain a reaction system; cooling the reaction system to room temperature, centrifugally separating, removing supernatant, washing with deionized water until the washing liquid is neutral, and drying to obtain the cuprous sulfide nanoflower containing copper defects, wherein the surfactant is trimethyl hexadecyl ammonium bromide.
2. The method for preparing cuprous sulfide nanoflower containing copper defects according to claim 1, wherein said method comprises the steps of: the strong base is a composite base consisting of potassium hydroxide and sodium hydroxide.
3. The method for preparing cuprous sulfide nanoflower containing copper defects according to claim 2, wherein said method comprises the steps of: the mass ratio of the potassium hydroxide to the sodium hydroxide is 2 (1-2).
4. The method for preparing cuprous sulfide nanoflower containing copper defects according to claim 1, wherein said method comprises the steps of: the mass ratio of the strong base to the water is 10 (1-5), the mass ratio of the surfactant to the water is 0.72 (1-5), the mass ratio of the elemental copper to the sodium sulfide is 2 (1-15), the mass ratio of the elemental copper to the water is 0.4 (1-5), and the volume ratio of the hydrazine hydrate to the water is 0.05 (1-5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910450346.4A CN110127749B (en) | 2019-05-28 | 2019-05-28 | A kind of preparation method of cuprous sulfide nanoflowers containing copper defects |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910450346.4A CN110127749B (en) | 2019-05-28 | 2019-05-28 | A kind of preparation method of cuprous sulfide nanoflowers containing copper defects |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110127749A CN110127749A (en) | 2019-08-16 |
| CN110127749B true CN110127749B (en) | 2021-09-24 |
Family
ID=67582353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910450346.4A Active CN110127749B (en) | 2019-05-28 | 2019-05-28 | A kind of preparation method of cuprous sulfide nanoflowers containing copper defects |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110127749B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683571B (en) * | 2019-09-27 | 2022-07-01 | 中国科学院合肥物质科学研究院 | Preparation method of flower-shaped cuprous sulfide micron particles |
| CN112536022B (en) * | 2020-11-22 | 2023-04-07 | 重庆交通大学 | CQDS/Cu 2 Preparation method of S nanoflower |
| CN112978798B (en) * | 2021-02-02 | 2022-12-16 | 昆明理工大学 | Method and device for preparing molybdenum oxide nano material with adjustable phase, shape and size |
| CN113394414B (en) * | 2021-06-16 | 2022-06-07 | 福州大学 | Construction of stamen-type S-doped manganese-copper electrocatalysts based on metal polyphenol-modified sodium alginate/nanocellulose composite aerogels |
| CN113788493B (en) * | 2021-09-18 | 2023-09-01 | 乌海瑞森新能源材料有限公司 | Microcapsule composite material, preparation method thereof and application thereof in lithium ion battery |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792173B (en) * | 2010-02-08 | 2011-12-14 | 许昌学院 | Chemical method for synthesizing flaky CuxSy nanocrystalline optoelectronic film controllably at low temperature |
| CN102807248B (en) * | 2012-07-13 | 2014-06-25 | 安徽师范大学 | Method for preparing cuprous sulfide nanoarray |
| CN103204536A (en) * | 2013-04-08 | 2013-07-17 | 华东师范大学 | Three-dimensional Cu2S@ZnO nano-heterostructure semiconductor material and its preparation method |
| CN104495908B (en) * | 2014-12-31 | 2016-06-08 | 湖南稀土金属材料研究院 | Cuprous sulfide raw powder's production technology and cuprous sulfide powder body |
| CN106082303A (en) * | 2016-06-07 | 2016-11-09 | 上海工程技术大学 | A kind of CuS material of flower-like structure and its preparation method and application |
| CN108126531A (en) * | 2017-12-28 | 2018-06-08 | 上海海事大学 | It is a kind of to contain Cu for light evaporation water2-xThe composite semipermeable membrane and its preparation and use of S |
| CN108659506A (en) * | 2018-05-04 | 2018-10-16 | 南京恒新新材料有限公司 | A kind of nanometer of cuprous sulfide composite electromagnetic shield materials and preparation method thereof |
| CN108682857B (en) * | 2018-06-14 | 2020-11-06 | 商丘师范学院 | A kind of preparation method of porous flower-shaped lithium battery cathode material |
| KR101977347B1 (en) * | 2018-10-01 | 2019-05-10 | 주식회사 앰트 | Copper sulfide core-shell nanoparticles including coating composition for selectively shielding near infrared ray and production of the same |
-
2019
- 2019-05-28 CN CN201910450346.4A patent/CN110127749B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110127749A (en) | 2019-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110127749B (en) | A kind of preparation method of cuprous sulfide nanoflowers containing copper defects | |
| CN102773110B (en) | Preparation method of coin-shaped hollow structure SnS2/SnO2 composite photocatalyst material | |
| CN106277064B (en) | A kind of method for preparing rhenium disulfide nanometer sheet | |
| CN100558639C (en) | A kind of double hydrolysis regulation prepares the method for basic lanthanum carbonate nano/micro crystal | |
| Ma et al. | Microwave synthesis of cellulose/CuO nanocomposites in ionic liquid and its thermal transformation to CuO | |
| CN102925979B (en) | Method for preparing perovskite lead titanate crystal nanosheet | |
| CN104058461A (en) | A kind of low-temperature preparation method of delafossite structure CuFeO2 crystal material | |
| CN108358234B (en) | A kind of copper hydroxychloride nano sheet and preparation method thereof | |
| CN105129857B (en) | A kind of flower-shaped tungsten oxide nanometer material and preparation method thereof | |
| CN107335452A (en) | The method that bismuth oxybromide ultrathin nanometer piece photochemical catalyst is synthesized under room temperature condition | |
| CN103819099A (en) | Method for preparing graphene structure-like copper-indium-sulfur nanosheet array membrane | |
| CN102259906A (en) | Method for preparing hollow zinc oxide microspheres | |
| CN102502793B (en) | A kind of preparation method of rod-shaped SnS nanocrystal | |
| CN110182770A (en) | A kind of preparation method of hydrophobic type hexagonal boron nitride nanosheet | |
| CN105669194B (en) | A kind of preparation method of vanadium dioxide thin sheet with thermally variable infrared emissivity | |
| CN107755691B (en) | A kind of preparation method of carbon coating copper micro-nano granules composite material | |
| CN107601441B (en) | Method for synthesizing tin selenide microcrystalline powder by hydrothermal method | |
| CN104532290A (en) | A kind of Fe2O3/ZnO homojunction material and its preparation method and application | |
| CN106379871B (en) | A kind of method for preparing two selenizing rhenium nanometer sheets | |
| CN105084409B (en) | It is a kind of（200）Crystal face exposes the synthetic method of single dispersing CuO nanometer sheet | |
| CN105271364A (en) | Method for preparing porous zinc oxide microspheres with metal organic skeleton MOF-5 materials being precursors | |
| CN110526228A (en) | The preparation method of one type petal-shaped carbon nanosheet | |
| CN101811677A (en) | Method for preparing hollow porous quadruped titanium nitride | |
| CN108033481A (en) | The preparation method of orienting stephanoporate copper sulfide nano material | |
| CN106277038B (en) | A kind of preparation method of micro-nano compound structure buergerite copper-zinc-tin-sulfur particulate |
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 |