CN103862062B - 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
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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 submicron carbon ball composite and its one-step method for synthesizing, particularly
Copper nano-particle with small size, high number density and high stability.Composite is by spherical carbon and the copper nanometer of high number density
Particle is constituted, and the copper particle overwhelming majority is evenly distributed in the inside of a diameter of 400-800nm carbon balls, and particle diameter in 5-50nm models
Enclose interior controllable.
Background technology
Copper nano material has boundless application in fields such as catalysis, sophisticated sensor and biologic medicals.Nanometer chi
The lower copper of degree is very active, it is easy to is oxidized inactivation, this feature limits their practical application.Compared with nanometer gold, silver,
Current research is remained in a great extent on the oxide and complex of copper.Prepare and preserve what copper nano material was used
Means often introduce protective atmosphere or cover surfactant protective layer.Under conditions of required precision height, grain is such as prepared
Even need to introduce high vacuum condition during copper nano-particle of the footpath scope between several nanometers to tens nanometers.Physical preparation method
Mainly include cluster sputtering method and high-temperature electric arc method,, mainly for the preparation of nano-level thin-membrane, the latter is in vacuum technique for the former
Grow up under support.The chemosynthesis of copper nano-particle compare the advantage of Physical to reduce copper ion as Main Means
It is that product uniformity is preferable, response parameter controllability is big, but the problem equally to be faced is how to prevent Oxidative inactivation.Avoid copper
Contact with oxygen, it is to solve this problem most straightforward approach that its oxidized speed is slowed down during aoxidizing.
The present invention will make the copper nano-particle generated in preparation process directly be scattered in protected material by introducing protection materials
Material is internal, is oxidized during preparation and preservation so as to be effectively prevented metallic copper nano particle.From carbon as protection
Material is compound with Nanometer Copper both will not to produce impact to metal performance itself, and its non-oxidizability is improve again.Using hydrothermal reduction
Method is embedded while copper nano-particle is synthesized to it.Reactant all in the form of solute in primary response liquid,
Reaction is carried out in the sealed reactor of High Temperature High Pressure.The characteristics of hydrothermal reduction synthetic method be product size and distribution all compared with
Uniformly, whole reaction solution system is substantially at homogeneous state, metal nanoparticle is reduced in the solution, nucleation, growth, crystal grain
Growth is more complete.Further, since the flooding mechanism of the homogeneous nucleation of hydro-thermal reaction and nonhomogen-ous nucleation mechanism and solid state reaction is not
Together, noval chemical compound and new material that other methods cannot be obtained can be createed.Clad is formed in preparation process in hydro-thermal method
In be easily achieved.
The invention discloses a kind of composite of copper nano-particle Uniform Doped submicron carbon ball and its one-step synthesis side
Method.In the case where not needing noble gases and any surfactant to protect, the preparation of nano level metal copper particle is realized
And its high stability.By adjusting solution PH, glucose (reducing agent and carbon source) and mantoquita (Cu2+Ion) molar concentration rate,
Reaction temperature and response time, it is possible to achieve the tune to the size of copper nano-particle, number density and distribution situation in composite particles
Control.
The content of the invention
The purpose of the present invention：The method for proposing to prepare the copper nano-particle with high thermal stability, particularly one-step synthesis
Method, obtains the composite being made up of the copper nano-particle of spherical carbon and high number density.The method is realized copper nanoparticle
Attached bag is embedded in amorphous carbon ball, so as to prevent the Oxidative inactivation of copper nano-particle；Simultaneously submicron spherical carbon granule causes to be combined
Material is easily separated, preserves and reused.The method is simple and convenient, can be generalized to other easy oxidation metal nanoparticles
Preparation field.
Technical scheme：Using glucose as reducing agent and carbon source, regulator of the ammonia as reaction system PH.
In concentration is for the D/W of 0.1-1.0M, a certain amount of mantoquita is dissolved, Cu is obtained2+Concentration is 12.5-20mM；In magnetic
Deca ammonia adjusts pH value to 4.5-6.0 under conditions of power stirring；Mixed solution is taken into reactor, in 160-180 DEG C of scope
Interior a certain constant temperature reacts 3-5 hours；Reactor naturally cools to room temperature, is to obtain target product, through being centrifuged repeatedly point
From with cleaning, finally in vacuum or N250 ± 10 DEG C of dryings under atmosphere, drying time 8-12 hours.
The present invention is that, with the mixed solution of glucose, copper nitrate and ammonia as raw material, preparation method is hydro-thermal method；Reactor
Filling rate is 50vol%；Composite is made up of the copper nano-particle of submicron spherical carbon and high number density, and carbon ball is a diameter of
400-800nm；The copper nano-particle overwhelming majority is evenly distributed in inside carbon ball；The number density of copper particle is adjustable, and size is in 5-
It is controllable in the range of 50nm；The protective effect of carbon causes copper nano-particle to have good non-oxidizability.
Prepare because part copper ion conversion is cuprammonium network and ion during mixed solution, solution is changed into deep from light blue
It is blue.
Stand after about 10-15min stirrings, the pH of solution will stablize unchanged.
Optimum preparating condition：3g glucoses are dissolved in deionized water the glucose solution for obtaining 0.38M；Copper ion concentration
Scope 12.5-20mM；Initial pH scopes 5.0-5.5；160 DEG C of reaction temperature, response time 3h, reactor filling rate 50vol%.
The raw material that hydro-thermal method is adopted is cheap glucose and nitric acid cupferron, and PH regulators and chelating agent are ammonia.
Glucose is selected to be carbonized the indefinite form carbon to be formed as protection materials in patent of the present invention, due to material with carbon element tool itself
There is higher chemical stability, copper particle on the one hand can be protected not contact with oxygen and aoxidize, another aspect glucose
The indefinite form carbon formed after carbonization is chemical all without occurring under normal temperature condition and higher temperature conditionss with oxygen and metallic copper
Reaction.
The present invention realizes amorphous carbon and embeds copper nano-particle to prevent its oxidized mistake using a step hydro-thermal reaction first
Purpose living；The step of overcoming template electrochemical deposition, templated chemistry vapour deposition and multistep processes is complicated, expensive etc. to be lacked
Point；Simultaneously submicron spherical carbon granule causes composite easily to separate, preserve and reuses.Copper nanometer in composite
The controllable such as size, number density, distributing position of particle.Without the need for any template, device is simple, easy to operate, can for the method
Control property it is good, easily accomplish scale production.Especially, the preparation field of other easy oxidation metal nanoparticles can be generalized to.This
Composite prepared by invention has huge using value in catalytic field.
Beneficial effects of the present invention：
(1) present invention firstly discloses the composite being made up of the copper nano-particle of spherical carbon and high number density, and copper
The controllable such as size, number density, distributing position of nanoparticle.
(2) adopt the mixed solution of glucose, copper nitrate and ammonia for raw material, in preparation process without the need for surfactant,
Template and protective atmosphere, by reaction system spontaneously forming for nano composite structure is realized, is simplified building-up process and is greatly reduced
Cost.
(3) present invention proposes skill that is a kind of simple, quick, economic and being applied to easy oxidation metal nanoparticle on a large scale
Art route.
(4) compared with other preparation methoies such as collosol and gel, hydro-thermal method has the following advantages：
1. controllability is good.By adjusting solution PH, glucose and mantoquita molar concentration rate, reaction temperature and response time,
The component of controllable product, size and architectural feature；
2. hydro-thermal method is simple, easy to operate, and yield is high；Preparation parameter controllability is good, it is easy to which product is regulated and controled.
3. it is with low cost, with good industrial applications prospect.
(5) embedding of carbon prevents reunion and the Oxidative inactivation of copper nano-particle, it is easier to separate, preserve and repeat to make
With.
Description of the drawings：
Fig. 1 schemes for (a-c) low power TEM figure and (d) HRTEM of sample Cu-C-1；A lower left corners illustration is compound for single Cu-C
The SAED figures of ball.
Fig. 2 amplifies TEM pictures for (a) low power TEM figure and (b) of sample Cu-C-2.
Fig. 3 amplifies TEM pictures for (a) low power TEM figure and (b) of sample Cu-C-3.
Fig. 4 is the XRD spectrum 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.
Specific embodiment
One step hydro thermal method prepares copper nano-particle Uniform Doped submicron carbon ball composite, specific embodiment party in the present invention
Formula is as follows：
Embodiment 1
The preparation of copper nano-particle Uniform Doped submicron carbon ball composite：4g glucoses are dissolved in 40mL deionized waters
The solution that concentration is 0.56M is configured to, then a certain amount of copper nitrate is added in solution, its molar concentration is 12.5mM, Deca
Ammonia adjusts the pH value of solution to 5.5 or so.Because part copper ion is changed into ammoniacal copper complex ion in solution, solution is by light blue
It is changed into navy blue.Through about 10-15min stirrings, 40mL mixed solutions are transferred in the reactor that volume is 50mL.Then will
Reactor is put in baking oven and reacts 5h at 180 DEG C.Reactor is naturally cooled to room temperature by reaction after terminating, through being centrifuged repeatedly
Separate and cleaning, finally in vacuum or N2The lower 50 DEG C of dryings of atmosphere, are dried 10 hours.Obtained sample is labeled as Cu-C-1.
Fig. 1 is (D/W concentration 0.55molL of embodiment 1-1, Cu2+Concentration 12.5mM, PH=5.5, compactedness
80%, 180 DEG C of reaction temperature, response time 5h) products therefrom (sample Cu-C-1) TEM pictures.Due to carbon ball diameter it is too big,
TEM figures can only see nanoparticle distribution (Fig. 1 a) at ball edge.Can see from the higher TEM figures of amplification, nanoparticle
Son is evenly distributed on the inside of carbon ball, and carbon ball surface only has a small amount of nanoparticle to there is (Fig. 1 b-c).Carbon ball diameter about 800nm,
And the electronic diffraction ring that the mean diameter of nanoparticle is respectively in 8nm, illustration is by a large amount of undersized in compound system
Copper nano-particle participates in the result of diffraction.High-resolution transmission electron microscopy (HRTEM) chart is bright, and single copper nano-particle is nearly ball
The monocrystal particle (Fig. 1 d) of shape.
Embodiment 2
D/W concentration 0.38molL-1, compactedness 50%, response time 3h, other conditions are with embodiment 1.
Obtained sample is labeled as Cu-C-2.
Fig. 2 is the TEM pictures of the products therefrom of embodiment 2.When concentration of glucose is reduced to 0.38M, compactedness is reduced to
50%, the response time is reduced to 3h, and the size of compound carbon ball is strongly reduced.A series of experimentation shows the concentration of glucose
The moderate dimensions (about in 400nm-800nm) of obtained composite balls during about 0.38M, and in composite balls copper nano-particle with very
High number density is evenly distributed.
Embodiment 3
D/W concentration 0.10molL-1, other conditions are with embodiment 2.
When D/W concentration is further decreased to 0.10molL-1, the mass fraction of copper in composite nano materials
It is decreased obviously, and distribution of the copper nano-particle in carbon ball becomes uneven under the conditions of being somebody's turn to do.
Embodiment 4
Cu2+It is 20mM that concentration increases, and PH increases to 6.05, and other conditions are with embodiment 2.Obtained sample is labeled as Cu-
C-3。
Fig. 3 is the TEM pictures of the products therefrom of embodiment 4.Work as Cu2+It is 20mM that concentration increases, and when PH increases to 6.05, is combined
The size of copper nano-particle substantially increases in ball, and average diameter is 45nm, and the number density of nanoparticle is substantially reduced.
Embodiment 5
Concentration of glucose is fixed on 0.38M, and copper ion concentration is 12.5-25mM, and other conditions are with example 2.
Pure carbon ball being prepared to glucose carbonization to compare, finding to add after mantoquita, the reaction rate of Glucose Carbon chemical conversion ball adds
Hurry up.The concentration of copper ion also has an impact for the size of copper nano-particle.Within the specific limits, with copper ion in reaction system
The rising of concentration, the size of copper nano-particle also has increase in product.Comparative sample Cu-C-2 (12.5mM) and sample Cu-C-3
(20mM) XRD spectrum, it can be seen that different copper ion concentrations, the halfwidth of correspondence product diffraction maximum is simultaneously differed, i.e. institute
The crystallite dimension for obtaining copper nano-particle is different.Additionally, the copper ion (25mM) of excess, the randomization that carbon ball can be caused to grow,
Show as the adhesion growth and rupture of carbon ball.Too low copper ion concentration can cause the uneven of copper nano-particle in final product
Distribution.Therefore the concentration of copper ion should be controlled in the range of 12.5-25mM.
Fig. 4 for sample Cu-C-1, Cu-C-2 and Cu-C-3 XRD spectrum.In 2 θ=43.5 °, 50.7 ° and 74.48 °
Position manifests XRD characteristic peaks, matches with the characteristic peak of Cu (111), (200) and (220) three crystal faces.Without obvious in collection of illustrative plates
CuO and Cu2The characteristic peak of the impurity such as O, shows the oxide that minimal amount of copper is not contained or may contained in obtained sample.
Most of copper are in the form of crystalline state particle in carbon ball matrix.Because sample is dried under vacuum condition low grade fever, often
Preserve under warm aerobic conditions, X-ray diffraction peak is demonstrated under room temperature aerobic conditions, and the copper nano-particle of carbon ball intrinsic silicon is not
It is oxidized.It can be seen that the position at correspondence peak is although identical in figure, but the halfwidth of characteristic peak is different.It is public by Scherrer
Formula calculating can approximately obtain the crystallite dimension of nanoparticle in sample Cu-C-1 and be about 9nm, the knot that this numerical value is characterized with TEM
Fruit is consistent.The particle diameter (30-50nm) of sample Cu-C-3 is significantly greater than sample Cu-C-1, this be due to the initial higher copper of reaction from
Sub- concentration.
Fig. 5 is x-ray photoelectron power spectrum (XPS) figure of the gained sample Cu-C-1 of example 1, to being embedded in carbon ball matrix surface
The oxidization condition of copper nano-particle is analyzed.Cu2p in figure1/2And Cu2p3/2Corresponding combination energy position is respectively
952.78eV and 932.71eV, has corresponded to respectively CuO (952.70eV) and Cu (932.70eV) and Cu2In O (932.70eV)
The energy levels of copper ion.The micro copper of analysis shows composite material surface has been oxidized to form the copper oxygen of monovalence and bivalence
Compound.
Embodiment 6
Add a large amount of ammonia, the pH for making initial soln modulates close neutrality, and other conditions are with example 1.
There is the carbon ball of shape distortion in sample, ball surface is not it is observed that copper nano-particle is present.
Appropriate ammonia (pH=11.5) is introduced in preparation process, pH value (the initial nitric acid of primary response solution is improved
Copper-glucose mixed solution is in faintly acid, and its pH value is about between 5.1-5.3), the original ph close 5.5 of solution is made, and it is molten
Most of copper ions are converted into the form of copper ammonia complexation ion in liquid.PH value in solution is adjusted to and is close to neutral suppression glucose
Polymerization dehydration carbonization.Find in preparation process, the carbon ball size that addition ammonia regulation PH is obtained is not added than same concentrations
The matched group of ammonia is little.Copper ammonia complexation ion is lower with respect to energy for copper ion, more stable in the solution, it is not easy to occur
Reduction reaction, thus the rate reduction that copper is reduced, the formation of nucleus after slow down, while being coated to form multiaspect by amino molecule
The copper ammonia complexation ionic charge density of body structure is less than copper ion, the absorption of the negative charge group of carbon ball surface branch terminals to it
Effect is little, and the speed of growth for making copper nano-particle slows down.With this understanding, the nucleus of formation has less size and preferably
Dispersibility.
The purpose that ammonia is introduced in reaction system is mainly carbon ball growth rate and copper ion during balancing response
Rate of reduction, is distributed with obtaining preferable carbon ball pattern with copper nano-particle.Appropriate ammonia can be effectively improved product
Pattern, its efficiency compares single regulation and control reaction reagent glucose and the mol ratio of copper nitrate will height.After amino molecule is introduced, copper is received
The uniformity of rice corpuscles distribution and the systematicness of nucleation are all high than not adding ammonia experimental group.Do not introducing ammonia
In reaction group, the copper crystal grain of free state can be formed toward contact, these copper crystal grain are not embedded in carbon ball or are embedded in carbon ball
On, but in the solution direct growth into the large-size particle for having certain crystal habit, this is for improving copper nano-particle
Dispersibility and specific surface area are unfavorable.Ammonia by the regulation to reaction solution PH and the impact to material existence form come
The growth of balance carbon ball and copper ion rate of reduction, so as to reach so that undersized copper nano-particle is uniformly distributed in carbon base body
Purpose.
Embodiment 7
At 160 DEG C of same temperature, the differential responses time (2h, 3h, 5h), other conditions are identical with example 1；
Same response time 3h, different temperatures is to (180 DEG C, 160 DEG C), and other conditions are identical with example 1.
Gained copper-carbon nano composite sphere size and copper nano-particle size all with the response time increase and
The rising of reaction temperature and increase.Higher reaction temperature improves the kinetic energy of molecules in solution, accelerates reaction rate, reaction
Process is directly proportional (reaction system is complicated organic chaining cyclization) to the time, and the thermodynamics that this point meets in chemical process are former
Reason, to guarantee that reaction can be carried out, temperature should be not less than 160 DEG C in experiment, and the response time is no less than 3h.
Claims (3)
1. a kind of one-step method for synthesizing of copper nano-particle Uniform Doped submicron carbon ball composite, it is characterised in that prepare
Concentration is 0.1-1.0molL-1D/W, be subsequently adding copper nitrate and stir to being completely dissolved, Cu is obtained2+It is dense
Spend for 12.5-20mmolL-1；Deca ammonia adjusts pH value to 4.5-6.0；Mixed liquor is proceeded to into the politef of reactor
In inner bag, filling degree is 40-50vol%, and then sealed reactor is put in constant temperature oven, and the response time is 3-5h, reaction
Carry out in atmosphere；After reaction terminates, naturally cool to room temperature, product be placed in vacuum drying oven Jing after being centrifuged repeatedly washing or
N2It is dried under protective atmosphere.
2. the one-step method for synthesizing of copper nano-particle Uniform Doped submicron carbon ball composite according to claim 1,
Characterized in that, the volume of reactor is 40-100mL, filling degree is 50vol%；Hydrothermal temperature is 160-180 DEG C of scope
Interior a certain steady temperature；Response time is 3-5h.
3. the one-step method for synthesizing of copper nano-particle Uniform Doped submicron carbon ball composite according to claim 1,
Characterized in that, by adjusting solution PH, glucose and mantoquita molar concentration rate, reaction temperature and response time, can be to multiple
The size of copper nano-particle, number density and distributing position are regulated and controled in condensation material；Product naturally cools to room temperature, Jing repeatedly from
It is placed in vacuum drying oven or N after heart washing2It is dried under protective atmosphere；50 ± 10 DEG C of baking temperature, drying time 8-12 hours.
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| 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 |
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| CN100463745C (en) * | 2007-06-13 | 2009-02-25 | 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 |
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