CN103862062A - Composite material of copper nano particles evenly doped with submicron carbon spheres and one-step synthesis method thereof - Google Patents
Composite material of copper nano particles evenly doped with submicron carbon spheres and one-step synthesis method thereof Download PDFInfo
- Publication number
- CN103862062A CN103862062A CN201410145522.0A CN201410145522A CN103862062A CN 103862062 A CN103862062 A CN 103862062A CN 201410145522 A CN201410145522 A CN 201410145522A CN 103862062 A CN103862062 A CN 103862062A
- Authority
- CN
- China
- Prior art keywords
- copper
- particle
- copper nano
- reaction
- nano particles
- 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.)
- Granted
Links
Images
Abstract
The invention discloses a composite material of copper nano particles evenly doped with submicron carbon spheres and a one-step synthesis method thereof. The composite material of the copper nano particles evenly doped with submicron carbon spheres is characterized in that the composite material is composed of the submicron carbon spheres and the high number density copper nano particles, and the diameter of each carbon sphere is 400-800 nm; most of the copper nano particles are evenly distributed in the carbon spheres; the number density of the copper particles is adjustable, and the size is controllable within the range of 5-50 nm; The protection effect of carbon enables the copper nano particles to have good inoxidizability. Dextrose water with the concentration being 0.1-1.0 mol L-1 is prepared, and the concentration of Cu2+ is 12.5-20 mmol L-1;ammonium hydroxide is dropped, and the PH value of the ammonium hydroxide is adjusted to be 4.5-6.0; the mixed liquor is transferred into a polytetrafluoroethylene inner container of a reaction kettle, and thermostatic reaction is conducted on the obtained mixed liquor in the reaction kettle in the temperature range of 160-180 DEG C for 3-5 hours; after reaction is completed, the mixed liquor is naturally cooled to the room temperature, products are repeatedly subjected to centrifugal washing and then are placed in a vacuum oven or under the protection atmosphere of N2 to be dried under the temperature 50+/-10 DEG C. The composite material of the copper nano particles evenly doped with submicron carbon spheres and the one-step synthesis method thereof solve the problems that metal copper, in particular the nano particles of the metal copper can be easily oxidized and can not be prepared and stored in a common environment easily.
Description
Technical field
The present invention relates to copper nano-particle Uniform Doped sub-micron carbon ball composite and one-step method for synthesizing thereof, particularly there is the copper nano-particle of small size, high number density and high stability.Composite is made up of the copper nano-particle of spherical carbon and high number density, and the copper particle overwhelming majority is evenly distributed in the inside that diameter is 400-800nm carbon ball, and particle diameter is controlled within the scope of 5-50nm.
Background technology
Copper nano material has boundless application in fields such as catalysis, sophisticated sensor and biologic medicals.Under nanoscale, copper is very active, is easy to oxidized inactivation, this characteristic limitations their practical application.Compared with nanometer gold, silver, current research still rests on the oxide and compound of copper to a great extent.The means that preparation and preservation copper nano material are used are usually to introduce protective atmosphere or covering surfaces activating agent protective layer.Under the high condition of required precision, during as the copper nano-particle of preparation particle size range between a few nanometer to tens nanometers, even need to introduce high vacuum condition.Physical preparation method mainly comprises cluster sputtering method and high-temperature electric arc method, and the former is mainly for the preparation of nanoscale film, and the latter grows up under the support of vacuum technique.The chemical synthesis of copper nano-particle is take reduction copper ion as Main Means, and the advantage of comparing Physical is that product homogeneity is better, and response parameter controllability is large, but the problem that will face is equally anti-oxidation inactivation how.Avoid contacting of copper and oxygen, in the process that oxidation occurs, slowing down its oxidized speed is to address this problem the most direct method.
The present invention will, by introducing protective material, make the copper nano-particle generating in preparation process directly be scattered in protective material inside, thereby effectively prevent that metallic copper nano particle is oxidized in the process of preparation and preservation.Select carbon as protective material and Nanometer Copper is compound neither can exert an influence to the performance of metal own, improved again its non-oxidizability.Adopt hydrothermal reduction method, in synthetic copper nano-particle, it is carried out to embedding.Reactant is all present in initial reaction liquid with the form of solute, and reaction is carried out in the sealed reactor of HTHP.The feature of hydrothermal reduction synthetic method is product size and distributes all more evenly, and whole reaction solution system is substantially in homogeneous state, metal nanoparticle reduction in solution, nucleation, growth, and grain growth is more complete.In addition,, because homogeneous nucleation and the heterogeneous mechanism of nucleation of hydro-thermal reaction are different from the flooding mechanism of solid phase reaction, can create noval chemical compound and new material that other method cannot obtain.In preparation process, form clad is easy to realize in hydro-thermal method.
The invention discloses a kind of composite and one-step method for synthesizing thereof of copper nano-particle Uniform Doped sub-micron carbon ball.In the situation that not needing inert gas and the protection of any surfactant, realize preparation and the high stability thereof of nano level metal copper particle.By regulator solution PH, glucose (reducing agent and carbon source) and mantoquita (Cu
2+ion) molar concentration rate, reaction temperature and reaction time, can realize the regulation and control of size, number density and distribution situation to copper nano-particle in composite particles.
Summary of the invention
Object of the present invention: propose to prepare the method, particularly one-step method for synthesizing of the copper nano-particle with high thermal stability, obtain the composite being formed by the copper nano-particle of spherical carbon and high number density.The method has realized copper nano-particle has been embedded in amorphous carbon ball, thereby prevents the oxidation inactivation of copper nano-particle; Submicron spherical carbon granule makes composite more easily separate, preserve and reuse simultaneously.The method is simple and convenient, can be generalized to the preparation field of other easy oxidation metal nano particle.
Technical scheme of the present invention: using glucose as reducing agent and carbon source, ammoniacal liquor is as the conditioning agent of reaction system PH.In the D/W that is 0.1-1.0M in concentration, dissolve a certain amount of mantoquita, make Cu
2+concentration is 12.5-20mM; Under the condition of magnetic agitation, dripping ammoniacal liquor regulates pH value to 4.5-6.0; Get mixed solution to reactor, a certain constant temperature reaction 3-5 hour within the scope of 160-180 ℃; Reactor naturally cools to room temperature, for obtaining target product, through centrifugation and cleaning repeatedly, finally at vacuum or N
2under atmosphere 50 ± 10 ℃ dry, drying time 8-12 hour.
The present invention be mixed solution take glucose, copper nitrate and ammoniacal liquor as raw material, preparation method is hydro-thermal method; Reactor filling rate is 50vol%; Composite is to be made up of the copper nano-particle of submicron spherical carbon and high number density, and carbon bulb diameter is 400-800nm; The copper nano-particle overwhelming majority is evenly distributed in carbon ball inside; The number density of copper particle is adjustable, and size is controlled within the scope of 5-50nm; The protective effect of carbon makes copper nano-particle have good non-oxidizability.
In preparation mixed solution process, because part copper ion conversion is cuprammonium network and ion, solution is from the light blue navy blue that becomes.
After about 10-15min stirs, leave standstill, the pH of solution will stablize unchanged.
Optimum preparating condition: 3g glucose is dissolved in the glucose solution that obtains 0.38M in deionized water; Copper ion concentration scope 12.5-20mM; Initial pH scope 5.0-5.5; 160 ℃ of reaction temperatures, reaction time 3h, reactor filling rate 50vol%.
The raw material that hydro-thermal method adopts is cheap glucose and copper nitrate reagent, and PH conditioning agent and complexing agent are ammoniacal liquor.
In patent of the present invention, select the indefinite form carbon of glucose carbonization formation as protective material; because material with carbon element itself has higher chemical stability; on the one hand can protect copper particle not contact and be oxidized with oxygen, can there is not chemical reaction in the indefinite form carbon forming after glucose carbonization on the other hand and oxygen and metallic copper under normal temperature condition and higher temperature conditions.
The present invention utilizes a step hydro-thermal reaction to realize amorphous carbon embedding copper nano-particle to prevent the object of its oxidized inactivation first; The step complexity of template electrochemical deposition, templated chemistry vapour deposition and multistep processes, the shortcoming such as expensive are overcome; Submicron spherical carbon granule makes composite more easily separate, preserve and reuse simultaneously.In composite, the size of copper nano-particle, number density, distributing position etc. all can regulate and control.The method is without any template, install simple, easy and simple to handle, controllability is good, easily accomplish scale production.Especially, can be generalized to the preparation field of other easy oxidation metal nano particle.Composite prepared by the present invention has huge using value in catalytic field.
Beneficial effect of the present invention:
(1) the present invention discloses the composite being made up of the copper nano-particle of spherical carbon and high number density first, and size of copper nano-particle, number density, distributing position etc. all can regulate and control.
(2) adopting the mixed solution of glucose, copper nitrate and ammoniacal liquor is raw material, in preparation process, without surfactant, template and protective atmosphere, relies on reaction system to realize the spontaneous formation of nano composite structure, simplifies building-up process and significantly reduces costs.
(3) the present invention proposes a kind of simple, fast, economical and be applicable to the technology path of easy oxidation metal nano particle on a large scale.
(4) compared with other preparation method such as such as collosol and gel, hydro-thermal method has the following advantages:
1. controllability is good.By regulator solution PH, glucose and mantoquita molar concentration rate, reaction temperature and reaction time, can control component, size and the architectural feature of product;
2. hydro-thermal method is simple, easy to operate, and productive rate is high; Preparation parameter controllability is good, is easy to product to regulate and control.
3. with low cost, there is good industrial applications prospect.
(5) embedding of carbon has prevented the reunion and oxidation inactivation of copper nano-particle, more easily separates, preserves and reuse.
Accompanying drawing explanation:
Fig. 1 is sample Cu-C-1's (a-c) low power TEM figure and (d) HRTEM figure; A lower left corner illustration is the SAED figure of single Cu-C composite balls.
Fig. 2 is sample Cu-C-2's (a) low power TEM figure and (b) amplifies TEM picture.
Fig. 3 is sample Cu-C-3's (a) low power TEM figure and (b) amplifies TEM picture.
Fig. 4 is the XRD collection of illustrative plates of sample Cu-C-1, Cu-C-2 and Cu-C-3.
Fig. 5 is the xps energy spectrum figure of sample Cu-C-1.
The specific embodiment
In the present invention, one step hydro thermal method is prepared copper nano-particle Uniform Doped sub-micron carbon ball composite, and the specific embodiment is as follows:
The preparation of copper nano-particle Uniform Doped sub-micron carbon ball composite: 4g glucose is dissolved in and is mixed with the solution that concentration is 0.56M in 40mL deionized water, in solution, add a certain amount of copper nitrate again, its molar concentration is 12.5mM, drips pH value to 5.5 left and right of ammoniacal liquor regulator solution.Because part copper ion in solution changes ammoniacal copper complex ion into, solution is from the light blue navy blue that becomes.Stir through about 10-15min, 40mL mixed solution is transferred in the reactor that volume is 50mL.Then reactor is put into baking oven and reacted 5h at 180 ℃.After reaction finishes, reactor is naturally cooled to room temperature, through centrifugation and cleaning repeatedly, finally at vacuum or N
2atmosphere lower 50 ℃ dry, dry 10 hours.Obtained identified as samples is designated as Cu-C-1.
Fig. 1 is embodiment 1 (D/W concentration 0.55molL
-1, Cu
2+concentration 12.5mM, PH=5.5, compactedness 80%, 180 ℃ of reaction temperatures, reaction time 5h) the TEM picture of products therefrom (sample Cu-C-1).Because carbon bulb diameter is too large, TEM figure can only see ball edge nano particle distribute (Fig. 1 a).The TEM figure higher from multiplication factor can see, nano particle is evenly distributed on the inside of carbon ball, and carbon ball surface only has a small amount of nano particle to have (Fig. 1 b-c).The about 800nm of carbon bulb diameter, and the average grain diameter of nano particle is respectively at 8nm, the electronic diffraction ring in illustration is the result that is participated in diffraction by a large amount of undersized copper nano-particles in compound system.High-resolution transmission electron microscopy (HRTEM) figure shows, single copper nano-particle is that (Fig. 1 d) for subglobose monocrystal particle.
D/W concentration 0.38molL
-1, compactedness 50%, reaction time 3h, other condition is with embodiment 1.Obtained identified as samples is designated as Cu-C-2.
Fig. 2 is the TEM picture of embodiment 2 products therefroms.In the time that concentration of glucose is reduced to 0.38M, compactedness is reduced to 50%, and the reaction time is reduced to 3h, and the size of composite carbon ball sharply reduces.A series of experimental study shows the moderate dimensions (greatly about 400nm-800nm) of the composite balls that the concentration of glucose makes while being about 0.38M, and in composite balls, copper nano-particle is evenly distributed with very high number density.
D/W concentration 0.10molL
-1, other condition is with embodiment 2.
When D/W concentration is further reduced to 0.10molL
-1, in composite nano materials, the mass fraction of copper obviously declines, and under this condition, the distribution of copper nano-particle in carbon ball becomes inhomogeneous.
Embodiment 4
Cu
2+concentration increases to 20mM, and PH is increased to 6.05, and other condition is with embodiment 2.Obtained identified as samples is designated as Cu-C-3.
Fig. 3 is the TEM picture of embodiment 4 products therefroms.Work as Cu
2+concentration increases to 20mM, and PH is increased at 6.05 o'clock, and in composite balls, the size of copper nano-particle obviously increases, and average diameter is 45nm, and the number density of nano particle reduces greatly.
Concentration of glucose is fixed on 0.38M, and copper ion concentration is 12.5-25mM, and other condition is with example 2.
To glucose, carbonization is prepared pure carbon ball and is compared, and finds to add after mantoquita, and Glucose Carbon changes into the reaction rate accelerates of ball.The concentration of copper ion also has impact for the size of copper nano-particle.Within the specific limits, along with the rising of copper ion concentration in reaction system, in product, the size of copper nano-particle also has increase.The XRD collection of illustrative plates of comparative sample Cu-C-2 (12.5mM) and sample Cu-C-3 (20mM), can find out different copper ion concentrations, and the halfwidth of corresponding product diffraction maximum is not identical, i.e. the crystallite dimension difference of gained copper nano-particle.In addition, excessive copper ion (25mM), can cause the randomization of carbon ball growth, shows as the adhesion growth of carbon ball and breaks.Too low copper ion concentration can cause the uneven distribution of copper nano-particle in end product.Therefore the concentration of copper ion should be controlled within the scope of 12.5-25mM.
The XRD collection of illustrative plates that Fig. 4 is sample Cu-C-1, Cu-C-2 and Cu-C-3.In 2 θ=43.5 °, the position of 50.7 ° and 74.48 ° manifests XRD characteristic peak, matches with the characteristic peak of Cu (111), (200) and (220) three crystal faces.In collection of illustrative plates, there is no obvious CuO and Cu
2the characteristic peak of the impurity such as O, in the sample that shows to make not containing or may contain the oxide of the copper of minute quantity.Most of copper is present in carbon ball matrix with the form of crystalline state particle.Because sample is all to dry under vacuum condition low-heat, under normal temperature aerobic conditions, to preserve, X-ray diffraction peak proved under normal temperature aerobic conditions, the copper nano-particle of carbon ball matrix inside is not oxidized.Although can find out in figure that the position at corresponding peak is identical, the halfwidth difference of characteristic peak.Calculated and can be similar to the crystallite dimension that obtains nano particle in sample Cu-C-1 and be about 9nm by Scherrer formula, this numerical value is consistent with the result of TEM sign.The particle diameter (30-50nm) of sample Cu-C-3 is obviously greater than sample Cu-C-1, and this is due to the initial higher copper ion concentration of reaction.
Fig. 5 is x-ray photoelectron power spectrum (XPS) figure of example 1 gained sample Cu-C-1, and the oxidation situation of the copper nano-particle that is embedded in carbon ball matrix surface is analyzed.Cu2p in figure
1/2and Cu2p
3/2corresponding combination energy position is respectively 952.78eV and 932.71eV, corresponding respectively CuO (952.70eV) and Cu (932.70eV) and Cu
2the energy levels of copper ion in O (932.70eV).Analysis shows the oxidized Cu oxide that has formed monovalence and divalence of the copper of composite material surface trace.
Embodiment 6
Add a large amount of ammoniacal liquor, make the pH modulation of initial soln approach neutrality, other condition is with example 1.
In sample, have the carbon ball of shape distortion, ball surface is failed to observe copper nano-particle and is existed.
In preparation process, introduce appropriate ammoniacal liquor (pH=11.5), (initial copper nitrate-glucose mixed solution is faintly acid to the pH value of raising initial reaction solution, its pH value is between 5.1-5.3), make the original ph of solution approach 5.5, and in solution, most of copper ions convert the form of cuprammonium complex ion to.PH value in solution is adjusted to and approaches the neutral glucose polymerisation dehydration carbonization that suppresses.In preparation process, find, the control group that the carbon ball size that interpolation ammoniacal liquor regulates PH to obtain is not added ammoniacal liquor than same concentrations is little.The relative copper ion energy of cuprammonium complex ion is lower, more stable in solution, be not easy to occur reduction reaction, thereby the rate reduction that is reduced of copper, the formation of nucleus after having slowed down, be less than copper ion by the coated cuprammonium complex ion charge density that forms polyhedral structure of amino molecule, the negative electrical charge group of a carbon ball surface chain end is little to its suction-operated, and the speed of growth of copper nano-particle is slowed down simultaneously.With this understanding, the nucleus of formation has less size and better dispersed.
Be mainly the rate of reduction of carbon ball growth rate and copper ion in balanced reaction process to the object of introducing ammoniacal liquor in reaction system, distribute to obtain the spherical looks of desirable carbon and copper nano-particle.Appropriate ammoniacal liquor can effectively improve the pattern of product, and its efficiency is compared the mol ratio of single regulation and control reaction reagent glucose and copper nitrate and wanted high.Introducing after amino molecule, the uniformity that copper nano-particle distributes and the systematicness of nucleation are all high than not adding ammoniacal liquor experimental group.In the reaction group of not introducing ammoniacal liquor, form the copper crystal grain of free state toward contact meeting, these copper crystal grain are not embedded in carbon ball or are embedded on carbon ball, but direct growth becomes to have the large-size particle of certain crystal habit in solution, this is disadvantageous for dispersiveness and specific area of improving copper nano-particle.Ammoniacal liquor comes the growth of balance carbon ball and copper ion rate of reduction by the adjusting on reaction solution PH and on the impact of material existence form, makes undersized copper nano-particle equally distributed object in carbon base body thereby reach.
Embodiment 7
At 160 ℃ of same temperatures, the differential responses time (2h, 3h, 5h), other condition is identical with example 1;
Same reaction time 3h, different temperatures is to (180 ℃, 160 ℃), and other condition is identical with example 1.
The size of copper-carbon nano composite sphere of gained and the size of copper nano-particle are all along with the increase in reaction time and the rising of reaction temperature and increase.Higher reaction temperature has improved the kinetic energy of molecules in solution, accelerate reaction rate, reaction process be directly proportional to the time (reaction system be complicated organic chaining Cheng Huan), this point meets the thermodynamic principles in chemical process, can carry out for guaranteeing reaction, in experiment, temperature should be not less than 160 ℃, and the reaction time is no less than 3h.
Claims (6)
1. copper nano-particle Uniform Doped sub-micron carbon ball composite and one-step method for synthesizing thereof, is characterized in that, composite is to be made up of the copper nano-particle of submicron spherical carbon and high number density, and carbon bulb diameter is 400-800nm; The copper nano-particle overwhelming majority is evenly distributed in carbon ball inside; The number density of copper particle is adjustable, and size is controlled within the scope of 5-50nm; The protective effect of carbon makes copper nano-particle have good non-oxidizability.
The one-step method for synthesizing of copper nano-particle Uniform Doped sub-micron carbon ball composite, is characterized in that, compound concentration is 0.1-1.0molL
-1d/W, then add mantoquita and be stirred to completely and dissolve, make Cu
2+concentration is 12.5-20mmolL
-1; Dripping ammoniacal liquor regulates pH value to 4.5-6.0; Mixed liquor is proceeded in the polytetrafluoroethylliner liner of reactor, filling degree is 40-80vol%, then sealed reactor is put into constant temperature oven, and the reaction time is 3-5h; After reaction finishes, naturally cool to room temperature, product is placed in vacuum drying oven or N through centrifuge washing repeatedly
2dry under protective atmosphere.
2. according to the copper nano-particle Uniform Doped sub-micron carbon ball composite described in claims 1, it is characterized in that, the copper nano-particle overwhelming majority is evenly distributed in the inside of carbon ball, only has a small amount of copper nano-particle on carbon ball surface.
3. the one-step method for synthesizing of copper nano-particle Uniform Doped sub-micron carbon ball composite according to claim 1, is characterized in that, adopts hydro-thermal method, and reaction is carried out in air; Take the mixed solution of glucose and mantoquita as presoma, wherein glucose is both as reducing agent, again as carbon source; Mantoquita comprises copper nitrate, copper sulphate or copper chloride, and ammoniacal liquor is as PH conditioning agent and Cu
2+complexing agent.
4. the one-step method for synthesizing of copper nano-particle Uniform Doped sub-micron carbon ball composite according to claim 1, is characterized in that, D/W concentration is 0.1-1.0molL
-1, copper ion concentration in mixed solution is 12.5-20mmolL
-1, drip ammoniacal liquor and regulate pH value to 4.5-6.0.
5. the one-step method for synthesizing of copper nano-particle Uniform Doped sub-micron carbon ball composite according to claim 1, is characterized in that, the volume of reactor is 40-100mL, and filling degree is 50vol%; Hydrothermal temperature is a certain steady temperature within the scope of 160-180 ℃; Reaction time is 3-5h.
6. the one-step method for synthesizing of copper nano-particle Uniform Doped sub-micron carbon ball composite according to claim 1, it is characterized in that, by regulator solution PH, glucose and mantoquita molar concentration rate, reaction temperature and reaction time, can regulate and control the size of copper nano-particle in composite, number density and distributing position; Product naturally cools to room temperature, is placed in vacuum drying oven or N through centrifuge washing repeatedly
2dry under protective atmosphere; 50 ± 10 ℃ of baking temperatures, drying time 8-12 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410145522.0A CN103862062B (en) | 2014-04-11 | 2014-04-11 | Composite material of copper nano particles evenly doped with submicron carbon spheres and one-step synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410145522.0A CN103862062B (en) | 2014-04-11 | 2014-04-11 | Composite material of copper nano particles evenly doped with submicron carbon spheres and one-step synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103862062A true CN103862062A (en) | 2014-06-18 |
| CN103862062B CN103862062B (en) | 2017-04-19 |
Family
ID=50901414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410145522.0A Expired - Fee Related CN103862062B (en) | 2014-04-11 | 2014-04-11 | Composite material of copper nano particles evenly doped with submicron carbon spheres and one-step synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103862062B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625660A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Reactive plugging agent for water-based drilling fluid and preparation method thereof |
| CN113101931A (en) * | 2021-03-22 | 2021-07-13 | 宝璟科技(深圳)有限公司 | Preparation method and application of modified carbon-coated copper nanoparticles carried by cupronickel |
| CN114436316A (en) * | 2020-11-03 | 2022-05-06 | 中国石油天然气集团有限公司 | Monodisperse flower-shaped copper oxide/carbon nano composite material and preparation method thereof |
| CN116536092A (en) * | 2023-03-30 | 2023-08-04 | 西北工业大学 | Carbon sphere@copper-based metal organic framework nano lubricant and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1774389A (en) * | 2003-04-17 | 2006-05-17 | 景垣实业株式会社 | Nano-structured metal-carbon composite and process for preparation thereof |
| CN101069928A (en) * | 2007-06-13 | 2007-11-14 | 湖南大学 | Method for preparing copper-base composite particles of internal carbon-inlaid nano pipe |
| KR100956505B1 (en) * | 2009-02-05 | 2010-05-07 | 주식회사 엘지화학 | Method of fabricating carbon particle/copper composites |
| CN102205422A (en) * | 2011-01-17 | 2011-10-05 | 深圳市圣龙特电子有限公司 | Nano copper powder for electronic paste and preparation process |
| CN102717093A (en) * | 2012-06-01 | 2012-10-10 | 黑龙江大学 | Preparation method for copper-carbon composite nanoparticle |
| CN103331452A (en) * | 2013-06-27 | 2013-10-02 | 北京科技大学 | Copper and carbon composite hollow sphere particle material and preparation method thereof |
-
2014
- 2014-04-11 CN CN201410145522.0A patent/CN103862062B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1774389A (en) * | 2003-04-17 | 2006-05-17 | 景垣实业株式会社 | Nano-structured metal-carbon composite and process for preparation thereof |
| CN101069928A (en) * | 2007-06-13 | 2007-11-14 | 湖南大学 | Method for preparing copper-base composite particles of internal carbon-inlaid nano pipe |
| KR100956505B1 (en) * | 2009-02-05 | 2010-05-07 | 주식회사 엘지화학 | Method of fabricating carbon particle/copper composites |
| CN102205422A (en) * | 2011-01-17 | 2011-10-05 | 深圳市圣龙特电子有限公司 | Nano copper powder for electronic paste and preparation process |
| CN102717093A (en) * | 2012-06-01 | 2012-10-10 | 黑龙江大学 | Preparation method for copper-carbon composite nanoparticle |
| CN103331452A (en) * | 2013-06-27 | 2013-10-02 | 北京科技大学 | Copper and carbon composite hollow sphere particle material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIAOLIANG ZHOU ET AL.: "In situ growth of copper nanocrystals from carbonaceous microspheres with electrochemical glucose sensing properties", 《MATERIALS RESEARCH BULLETIN》 * |
| YI CHENG ET AL: "Hydrothermal Synthesis of Cu@C Composite Sphere by a One-Step Method and Their Use as Sacrificial Templates to Synthesis a CuO@SiO2 Core-Shell Structure", 《EUROPEAN JOURNAL OF INORGANIC CHEMISTRY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625660A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Reactive plugging agent for water-based drilling fluid and preparation method thereof |
| CN112625660B (en) * | 2019-09-24 | 2023-01-31 | 中国石油化工股份有限公司 | Reactive plugging agent for water-based drilling fluid and preparation method thereof |
| CN114436316A (en) * | 2020-11-03 | 2022-05-06 | 中国石油天然气集团有限公司 | Monodisperse flower-shaped copper oxide/carbon nano composite material and preparation method thereof |
| CN113101931A (en) * | 2021-03-22 | 2021-07-13 | 宝璟科技(深圳)有限公司 | Preparation method and application of modified carbon-coated copper nanoparticles carried by cupronickel |
| CN116536092A (en) * | 2023-03-30 | 2023-08-04 | 西北工业大学 | Carbon sphere@copper-based metal organic framework nano lubricant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103862062B (en) | 2017-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tong et al. | Polymorphous ZnO complex architectures: selective synthesis, mechanism, surface area and Zn-polar plane-codetermining antibacterial activity | |
| CN100534675C (en) | Method for preparing spherical nano silver powder | |
| CN107413354B (en) | Preparation method of silver-loaded copper oxide nanocomposite | |
| CN109650424B (en) | Amorphous alumina octahedral particle and preparation method thereof | |
| CN108620601B (en) | Method for preparing flaky Cu nanocrystalline at room temperature | |
| Baqer et al. | Copper oxide nanoparticles synthesized by a heat treatment approach with structural, morphological and optical characteristics | |
| CN106363166B (en) | A kind of nanometer of La2O3Uniform Doped nanometer molybdenum composite powder and preparation method thereof | |
| CN103862062A (en) | Composite material of copper nano particles evenly doped with submicron carbon spheres and one-step synthesis method thereof | |
| CN105127441A (en) | Preparation method of platinum nanocrystalline dispersion system | |
| CN111905796A (en) | Preparation method of superfine metal nanoparticle/carbon nitride nanosheet composite material | |
| CN110104623A (en) | A kind of preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape | |
| Tiong et al. | Polyacrylic acid assisted synthesis of Cu2ZnSnS4 by hydrothermal method | |
| CN105800604A (en) | Preparation method of graphene-loaded cobalt ferrite quantum dot | |
| Zhou et al. | Synthesis of γ-MnOOH nanorods and their isomorphous transformation into β-MnO 2 and α-Mn 2 O 3 nanorods | |
| KR101509332B1 (en) | Preparation of copper selenide compound controlling particle size and composition | |
| CN108328634A (en) | A kind of copper load zinc aluminate nano-powder and preparation method thereof | |
| CN101531403B (en) | Method for preparing cobaltosic oxide single-dimensional nano material | |
| CN101525148A (en) | Method for preparing cupric oxide one dimension nano material | |
| CN101525158B (en) | Method for preparing ferric oxide one dimension nano material | |
| CN113697780B (en) | Preparation method of pH-regulated bismuth telluride nanowire | |
| CN111347060A (en) | Preparation method of nano-silver colloid with controllable particle size | |
| CN111234248A (en) | Method for synthesizing size-adjustable metal complex microspheres from Schiff base and metal complex microspheres | |
| CN114105107B (en) | Highly monodisperse MoSe with different morphologies 2 Method for preparing nano material | |
| CN101665984B (en) | Copper zinc alloy nanowire and preparation method thereof | |
| CN105776197A (en) | Surface porous graphene material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170419 Termination date: 20190411 |