CN104986762B - Synthetizing method of diamonds - Google Patents
Synthetizing method of diamonds Download PDFInfo
- Publication number
- CN104986762B CN104986762B CN201510477824.2A CN201510477824A CN104986762B CN 104986762 B CN104986762 B CN 104986762B CN 201510477824 A CN201510477824 A CN 201510477824A CN 104986762 B CN104986762 B CN 104986762B
- Authority
- CN
- China
- Prior art keywords
- diamond
- graphene
- compound
- synthetic method
- solid
- 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
Abstract
The invention relates to a synthetizing method of diamonds, and belongs to the technical field of new materials and the application thereof. The synthetizing method comprises the following technologies of: (1), performing mixing: mixing a metal organic compound and/or a coordination compound with an auxiliary; (2), performing heating: heating the mixture obtained in the step (1); and (3), performing separation and purification: sequentially placing products obtained in the step (2) in an acidic solution and/or an oxidisability solution for regurgitation, and removing graphene microchips and impurities so as to obtain the diamonds. The synthetizing method disclosed by the invention is simple and direct in fabrication process, the diamonds are synthetized at a low temperature, and the investment cost and the operating cost of equipment are reduced, so that the production cost of the diamonds is greatly reduced.
Description
Technical field
The present invention relates to a kind of synthetic method of diamond, belongs to new material and its applied technical field.
Background technology
Diamond static ultrahigh pressure (50～100kb, i.e. 5～10GPa) and high temperature (1100～3000 °C) technology
By the carbon raw materials such as graphite and some metals（Alloy）Reaction generate diamond, its typical crystalline state be cube (hexahedron),
Octahedra and six-octahedra and their transitional form.Industrially show the mainly static pressure menstruum of significant application value
Method.The yield of the abrasive material level diamond for obtaining in this way has exceeded natural diamond.
Additionally, the method for diamond also has epitaxy：Using the carbon being pyrolyzed and separate out when being electrolysed some carbonaceous materials
Source diamond seeds or some rise.Chemical vapour deposition technique：It is hydrocarbon
Compound decomposes at a certain temperature, and gas-phase carbon forms the work of the thin film with diamond crystal structures in substrate deposit
Process.Physical vaporous deposition：Under vacuum, using low-voltage, the arc-discharge technique of high current is put using gas
Electricity makes target evaporate and make by evaporant（Graphite）Occur to ionize with target, using the acceleration of electric field, make by evaporated material
And its product is evaporated on workpiece.Epitaxy is commonly used to synthesize big crystal grain diamond, and chemical vapour deposition technique is commonly used to close
Into diamond thin, physical vaporous deposition is commonly used to synthesize diamond like carbon film.
It is pointed out that artificially synthesizing diamond needs high pressure high temperature device, such as hinge type cubic hinge press, two sides
Top pressure ultra-high pressure apparatus, year wheeled high pressure high temperature device, barrel-shaped metal pressure container（Explosion method）.Due to the height of manufacturing cost
The restriction of high and crystalline size and shape, is industrially mainly used in superabrasive.
Tested according to high-pressure physics and theory analysis, when graphite is changed into diamond, participated in no metal (or alloy)
In the case of, need the high temperature of the pressure and more than 2700K of 13GPa.With the development of science and technology, people have found one more
Plus practicable approach：Add metal (or alloy) to promote the process that non-diamond carbon changes to diamond, exactly draw
Enter metal (or alloy), greatly reduce the pressure and temperature of artificially synthesizing diamond.Because of metal (or alloy)
Effect, correspondingly makes synthesis pressure and temperature be reduced to the pressure and 1200 DEG C or so scopes or lower of 10GPa to 4GPa, presses
Power, temperature are relevant with the species of the metal (or alloy) selected.
The commercial production of diamond, the difficult problem for facing remain high-temperature high-pressure apparatus and consume serious problem, solve this
The method of problem has two：One quality for being to improve high-temperature high-pressure apparatus, but it is very high from the cost for solving this problem；It is another
Individual is further to reduce diamond synthesizing pressure and temperature, but the catalyst suitable for low-temp low-pressure condition diamond synthesis has no
Report.Catalyst is added just to make us be possible to the reaction temperature of artificially synthesizing diamond to reduce, with reaction temperature
Reduce, certainly corresponding reaction pressure can also be reduced.
The theoretical foundation of Catalyst Design：
1. Structure adaptation principle：This shows that structural agent plays very big effect in catalysis.It is now acknowledged, chemistry
Masterpiece is carried out under exerting oneself, and this chemical force is that the chemical bond of certain length (between atom) and energy (dissociation energy) is represented.Due to
The sphere of action of chemical force is little, and atom could interact only when which contacts with each other, and is not all of during the course of the reaction point
Son all participates in reaction greatly, and only has those individual atoms for contacting with each other to work, and in catalytic reaction, reaction of atomic should also be with
Catalyst is contacted.
2. energy adaptation principle：In catalytic reaction, its energy adaptation principle is the most important foundation for selecting catalyzer contact agent.Urge
Agent must have adsorption to reaction molecular in addition to meeting the requirement of crystal structure adaptation, and this chemical action is adsorbed
Power can not be too little, can not otherwise make the chemical bond to be ruptured fully relax;But can not be too big, otherwise product is difficult desorbing.
3. the theoretical substance of intermediate complex is：It is assumed that catalyst participates in reaction generates unstable network with reactant
Compound.Intermediate complex is easily formed, and is also easily decomposed.Intermediate complex is formed makes reaction easily carry out.It is known that by stone
It is very slow that black (A) is translates directly into the speed of diamond (B).If adding catalyst K, this reaction just to greatly accelerate, its
Reason is that A is combined with K and generated intermediate product AK.The atom (or therein several) of graphite is risen and between the atom of catalyst
Interaction weaken the adhesion between graphite respective atoms inside.When adsorbing on a catalyst between graphite respective atoms inside
Distance there occurs change, occurred as soon as significant molecular shape change, the i.e. graphitic molecules in adsorbed state and wanted specific ionization state
Shi Rongyi reacts.
Can help to destroy graphite lattice and set up diamond lattice catalyst have the 8th race's element of periodic chart and Cr, Ta,
Mn, Ge, and the compound of above element such as nickel oxide, ferric chloride, CoFe6, CoMn13Ni12, NiMn, NiFe, NiCu,
Ni80Cr20, Ni70Cr15Fe8, Ni70Mn25Co5Deng.
The non-eight races element of a few classes and its alloy can do high pressure high temperature growth diamond catalyst：The first kind：Composite catalyst,
Form carbide formers (Ti, Zr, Hf, V, Nb, Mo, W), plus carbide formers (Cu, Ag, Au) can not be formed；Equations of The Second Kind：
Mg；3rd class：Wrap oxygen containing material Li2CO3、Na2CO3、SrCO3、CaCO3、MgCO3、Na2SO4、MgSO4·2H2O、Mg(OH)2、
Ca(OH)2·H2O;4th class：Inert element P, Cu, Zn, Ge, Sn, Sb；5th class：Hydrogen-containing compound LiH, CaH2.These changes
Compound does catalyst growth diamond needs 1870K temperatures above, 7.0GPa pressure above not to adopt for commercial production.
Graphene has preferable monoatomic layer two dimensional crystal structure, is made up of hexagonal lattice, this special structure
Impart the unique calorifics of grapheme material, mechanics and electric property.At present, Graphene is applied to into lithium ion battery battery
The aspects such as pole material, ultracapacitor, electrode of solar battery material, hydrogen storage material, sensor, optical material, pharmaceutical carrier,
Illustrate the wide application prospect of grapheme material.Outer-shell electron forms the carbon-carbon double bond formed by the carbon atom of sp2 hydridization（C=
C）It is one of most strong valence link of nature, according to its bond energy 607KJ/mol and the density of carbon key, calculates the springform of Graphene
Measure as 1Tpa (1 TPa=103 GPa=106MPa).According to Ji Laman（Gilaman）The calculating of solid material theory inherent strength
Can draw, the tensile strength of Graphene is 180GPa.And general block iron and steel, including various different trade mark carbon steels and rustless steel
Including, its intensity is between 0.78-1.68GPa, therefore the intensity of Graphene is about more than 100 times of common iron and steel.
A paper in " science " magazine（2008. Vol. of Science, 18 July, 321. no. 5887, pp.
385-388, " Measurement of the Elastic Properties and Intrinsic Strength of
Monolayer Graphene）, physicss scholar Changgu Lee of the author for Columbia University, James Hone etc., he
The mechanical characteristic of Graphene has been carried out relatively to study comprehensively.For this purpose, the Graphene that they choose some 10-20 microns is studied
These Graphene samples have first been placed on a surface and have been bored on foraminate crystal thin plate by object, and the diameter of this some holes is in 1-1.5
Between micron.Then pressure is applied to the Graphene being placed on aperture with probe made by diamond, tests bearing for they
Ability.As a result find, before Graphene sample starts fragmentation, which is reached per the maximum pressure that 100 nanometers of distances can above be born
About 2.9 micro- cattle.According to measuring and calculating, this result can just make 1 meter long of Graphene rupture equivalent to the pressure that will apply 55 newton.Such as
Fruit can produce out thickness equivalent to bread and cheese plastic packaging bag（About 100 nanometers of thickness）Graphene, then need to apply poor
The pressure of few 20,000 newton could be pulled apart.
To sum up, if making container with Graphene, for diamond, due to the voltage endurance of Graphene container, can
To bear the pressure more much bigger than existing diamond device, such that it is able to substantially reduce the temperature needed for diamond.
What the preparation method of grapheme material had been reported has：Mechanical stripping method, chemical oxidization method, crystal epitaxy method,
Chemical vapour deposition technique, organic synthesis method and CNT stripping method etc..
1st, micromechanics stripping method
2004, Geim etc. used micromechanics stripping method first, successfully from highly directional thermal cracking graphite (highly
Oriented pyrolytic graphite) on peel off and observe single-layer graphene.Geim seminar using this method into
Work(is prepared for quasi- two-dimensional graphene and observes its pattern, the reason for disclosing Graphene two dimensional crystal structure and exist.Micromechanics
Stripping method can prepare high-quality graphene, but there is the deficiency of low yield and high cost, be unsatisfactory for industrialization and scale
Production requirement, can only be prepared as laboratory at present on a small scale.
2nd, chemical vapour deposition technique
Chemical vapour deposition technique (Chemical Vapor Deposition, CVD) is first in prepare with scale Graphene
There is new breakthrough in terms of problem.CVD refers to that reacting substance issues biochemical reaction in gaseous condition, generates solid matter and sinks
Product is on the solid matrix surface of heating, and then the Technology of solid material is obtained.
Kong of the Massachusetts Institute of Technology etc., Korea are being utilized into the Hong etc. of Jun Guan universities and the Chen etc. of Purdue University
CVD prepares Graphene.They use a kind of simple cvd furnace of tubulose with nickel as substrate, are passed through carbonaceous gas, such as：Carbon
Hydrogen compound, it resolves into the surface that carbon atom is deposited on nickel at high temperature, forms Graphene, by slight chemical etching,
Make graphene film and the isolated graphene film of nickel sheet.This thin film electrical conductivity when light transmittance is 80% can reach 1.1
× 106S/m, becomes the potential succedaneum of current transparent conductive film.The large-area graphite of high-quality can be prepared with CVD
Alkene, but the preferably expensive of substrate material monocrystalline nickel, this possibly affect Graphene industrialized production it is important because
Element.CVD can meet the requirement of prepare with scale high-quality graphene, but relatively costly, complex process.
3rd, oxidation-reduction method
Oxidation-reduction method preparation cost is cheap and easy realization, becomes the best approach for preparing Graphene, and can make
Standby stable graphene suspension, solves Graphene and is difficult scattered problem.Oxidation-reduction method refer to by native graphite with it is strong
Acid and oxidizing species reaction generate graphite oxide (GO), are prepared into graphene oxide (mono-layer oxidized stone through ultrasonic disperse
Ink), the oxy radical on addition reducing agent removal graphite oxide surface, such as carboxyl, epoxy radicals and hydroxyl obtain Graphene.
After oxidation-reduction method is suggested, laboratory is become with its simple technique and prepares the most easy of Graphene
Method, obtains the favor of vast Graphene researcher.Ruoff etc. is had found by adding chemical substance such as Dimethylhydrazine, to benzene two
Phenol, sodium borohydride (NaBH4) and liquid hydrazine etc. remove the oxy radical of graphene oxide, can just obtain Graphene.Oxidation-reduction method
Stable graphene suspension can be prepared, solves the problems, such as that Graphene is difficult to disperse in a solvent.
The shortcoming of oxidation-reduction method is that magnanimity preparation easily brings waste liquor contamination and the Graphene for preparing to there is certain lacking
Fall into, for example, the fault of construction of the topological defect such as five-membered ring, heptatomic ring or presence-OH groups, these will cause Graphene part electricity
The property learned loss of energy, is restricted the application of Graphene.
4th, solvent stripping method
The principle of solvent stripping method is the dispersion liquid that low concentration is formed by a small amount of graphite dispersion in solvent, using super
The Van der Waals force of the action breaks down graphite layers of sound wave, now solvent may be inserted into graphite layers, peeled off layer by layer, prepared
Graphene.The method will not destroy the structure of Graphene as oxidation-reduction method, can prepare high-quality Graphene.
The yield highest (about 8%) of Graphene in N-methyl ketopyrrolidine, electrical conductivity is 6500S/m.Research finds highly directional hot tearing
Solution graphite, thermal expansion graphite and crystallite Delanium are suitable for solvent stripping method and prepare Graphene.Solvent stripping method can be made
Standby high-quality Graphene, the no any defect of surface introducing in Graphene of the process that whole liquid phase is peeled off is which in micro- electricity
The application in the fields such as sub-, multifunctional composite provides wide application prospect.Have the disadvantage that yield is very low.
5th, solvent-thermal method
Solvent-thermal method is referred in special closed reactor (autoclave), using organic solvent as reaction medium, is led to
Cross and reaction system is heated to into critical temperature (or being close to critical temperature), itself produces high pressure and carries out material in reaction system
A kind of effective ways for preparing.
Solvent-thermal method solves the problems, such as prepare with scale Graphene, while also bringing the very low negative shadow of electrical conductivity
Ring.To solve the deficiency thus brought, solvent-thermal method and oxidation-reduction method are combined and have prepared high-quality stone by researcher
Black alkene.The graphene film resistance that under the conditions of the discovery solvent thermal such as Dai prepared by redox graphene is made less than under conventional conditions
Standby Graphene.The characteristics of solvent-thermal method is because preparing high-quality graphene under high-temperature and high-pressure enclosing system is increasingly by scientist's
Concern.The combination of solvent-thermal method and other preparation methoies will become the another bright spot of Graphene preparation.
6th, other methods
The preparation method of Graphene also has high temperature reduction, photoreduction, epitaxial crystal growth method, microwave method, arc process, electricity
Chemical method etc..The author more than on the basis of propose that a kind of Mechanical Method prepares the new method of nano-graphene microplate, and attempt magnanimity
Preferable achievement is obtained in the research of production Graphene.How the advantage of the various graphene preparation methods of integrated use, takes long benefit
It is short, the insoluble and instable problem, perfect frame and electrical property etc. for solving Graphene be the focus studied from now on and
Difficult point, the also preparation and synthesis for Graphene from now on open up new road.
The basis that high-quality Graphene crystalline material is all applications, the simple controllable chemistry of development are prepared on a large scale
Preparation method is the most convenient, feasible approach.
The content of the invention
It is an object of the invention to the characteristic for utilizing Graphene intensity high, there is provided a kind of processing technology is simple and direct, at low temperature
Diamond synthesis, reduce the cost of investment and operating cost of equipment, so as to substantially reduce the diamond of diamond production cost
Synthetic method.
The reaction principle of diamond synthesizing method of the present invention is：Auxiliary agent and metallo-organic compound and/or ligand compound
Thing mix homogeneously, in heating process, metallo-organic compound and/or coordination compound form Graphene or graphene microchip,
Cladding auxiliary agent forms capsule, continues heating, and auxiliary agent gradually decomposes, and releases gas, and capsule pressure gradually increases, and Graphene is micro-
Piece is pressurized, and diamond is converted in the presence of metallic catalyst.
The present invention is achieved through the following technical solutions：
A kind of synthetic method of diamond, which is characterized in that and comprises the following steps：
1）, mixing
Metallo-organic compound and/or coordination compound are mixed with auxiliary agent；
2）, heating
To step 1）The mixture of gained is heated；
3）, isolate and purify
By step 2）The product for obtaining flows back in being sequentially placed into the solution of acidity and/or oxidisability, removes graphene microchip
And impurity, obtain diamond；
Step 1）The metallo-organic compound is also known as metallo-organic compound.Alkyl（Including methyl, ethyl, propyl group, fourth
Base etc.）And aromatic radical（Phenyl etc.）The compound that combines to form of alkyl and metallic atom, and carbon is straight with metallic atom
The general name of the material that binding is closed；
Step 1）Described metallo-organic compound be polyoxometallate organic compound, described polyoxometallate
It is the class multi-metal oxygen cluster compound formed by oxygen connection by early transition metal ion；
Step 1）There is the compound of characteristic chemical structure for a class, by central atom or ion in the coordination compound
The molecule or ion that are referred to as ligand with around it, is combined to form by coordinate bond wholly or in part.
The coordinate bond is chemical bond present in coordination compound, provides two electronics of bonding by an atom, into
For electronq donor, another bonding atom then becomes electron acceptor.
The auxiliary agent is carbonate, and carbonate is the salt that metallic element cation is mutually bound up with carbonate, described
Carbonate can divide normal salt M2CO3, acid salt MHCO3And subcarbonate M2(OH)2CO3（M is metal）Three classes.The carbonate
Including but not limited to Li2CO3、Na2CO3、K2CO3、Rb2CO3、Cs2CO3、MgCO3、CaCO3、SrCO3、BaCO3In one or more
Mixing.
Step 1）In mixed process, first metallo-organic compound and/or coordination compound are dissolved in solvent, are subsequently adding
Auxiliary agent, stirs, and then removes solvent, obtains solid mixture；
The solvent is water, ionic liquid, organic solvent, one or more mixing in supercritical fluid；
Step 1）In described mixed process, metallo-organic compound and/or coordination compound and auxiliary agent directly mix, so
Afterwards grind and/or stir by way of mix homogeneously；
Step 1）Described metallo-organic compound and/or coordination compound and auxiliary agent are 1 according to mass ratio：n (0.1≤
n≤10）Mixing；Metallo-organic compound and coordination compound are 1 according to mass ratio：n (0.1≤n≤10）Mixing.
Step 1）In described mixed process, metallo-organic compound and/or coordination compound and auxiliary agent directly mix, so
Afterwards grind and/or stir by way of mix homogeneously；
Step 2）In described heating process, protective gas need to be passed through into heater or will be heated before heating
Device is evacuated to vacuum；
The protective gas is one or more mixing in nitrogen, helium, argon, neon, Krypton and xenon；
Step 2）In described heating process, heating and temperature control is at 400 DEG C to 1000 DEG C.
Step 2）In described heating process, Stress control is in 0.1 to 100MPa.
Step 2）In described heating process, 10 minutes to 10 hours heat time heating time.
Step 3）Described purification procedures are：By step 2）The product for obtaining is cooled to room temperature, is subsequently placed in dense salt
Flow back in acid, be subsequently cooled to room temperature, centrifugation takes solid, is washed till neutrality, then be centrifuged and take solid, by what is obtained
Solid is placed in perchloric acid and flows back, and in bottle, black disappears, and after backflow terminates, is cooled to room temperature, and centrifugation takes solid,
And deionized water is washed till neutrality and dries, and obtains final product diamond.
The present invention adopts metallo-organic compound or coordination compound as the carbon source and catalyst of artificially synthesizing diamond,
Metallo-organic compound or coordination compound can regard the intermediate complex of carbon and catalyst as, can substantially reduce diamond
The temperature and pressure of synthesis, and the present invention first generates graphene microchip in the building-up process of diamond, using high intensity
Graphene maintains the pressure inside reaction system, thus does not need extra pressurizer.And diamond synthesis traditional method is adopted
With engine driven supercharging, equipment investment and equipment attrition are larger.Technical solution of the present invention is compared with existing like product or method and has
Advantage or the Advantageous Effects that can be reached：1. relatively the industrial high temperature and high pressure method for adopting and explosion method synthesize Buddha's warrior attendant at present
Stone, present invention diamond synthesis under low-temp low-pressure（Can be 600 DEG C or so, the pressure of 0.1MPa）, reduce the throwing of equipment
Money cost and operating cost, greatly reduce the production cost of diamond.2. technical solution of the present invention, the diamond surface of synthesis
Product is big, and surface activity is high, is easily prepared into composite.
Description of the drawings
Fig. 1：The transmission electron microscope photo of diamond-graphene microplate complex of the present invention；
Fig. 2：The stereoscan photograph of diamond-graphene microplate complex of the present invention.
Specific embodiment
The specific embodiment of the present invention is provided below with reference to accompanying drawing, for the present invention is described further.
Embodiment 1
The method for preparing diamond of the present embodiment, comprises the following steps：
1st, by binuclear cluster complexes and Calcium Carbonate mix homogeneously.
Binuclear cluster complexes（1 gram）It is dissolved in 50 milliliters of water（Device is beaker）, it is subsequently adding Calcium Carbonate（1 gram）Stirring
Uniformly（Device is magnetic stirring apparatuss）, then water is evaporated obtains solid mixture（Device is Rotary Evaporators）.Then, by solid
Mixture grind into powder（Device is Achatess beveller）.
2nd, the mixture pyrolysis of binuclear cluster complexes and Calcium Carbonate are generated into diamond and graphene microchip.
Next, resulting mix powder is put in tube furnace, in nitrogen atmosphere, pressure is that a standard is big
Air pressure, is heated to 800 degrees Celsius and is incubated two hours.
3rd, thermal decomposition product is processed, obtains product
It is after heating terminates, to be cooled to room temperature, mixture is flowed back 20 hours in concentrated hydrochloric acid（Device is flask add-back stream
Condensing tube）.After backflow terminates, room temperature is cooled to, centrifugation takes solid, and deionized water is washed till neutrality.It is then centrifuged for
Separation takes solid, and resulting solid is flowed back in perchloric acid, and in bottle, black disappears.After backflow terminates, it is cooled to
Room temperature, centrifugation take solid, and deionized water is washed till neutrality and dries（Device is centrifuge and baking oven）.Product is Buddha's warrior attendant
Stone.The transmission electron microscope photo of non-purification diamond is shown in accompanying drawing 1, and in figure, interplanar distance is 0.206 nanometer, is diamond（111）
Crystal face.The stereoscan photograph of diamond-graphene microplate complex is shown in accompanying drawing 2, is the octahedron crystallization of diamond in figure.
Embodiment 2
The method for preparing diamond of the present embodiment, comprises the following steps：
1st, by iron porphyrin and Calcium Carbonate mix homogeneously；
Iron porphyrin（1 gram）It is dissolved in 250 milliliters of dichloromethane（Device is beaker）, it is subsequently adding Calcium Carbonate（1 gram）Stirring
Uniformly（Device is magnetic stirring apparatuss）, then dichloromethane is evaporated obtains solid mixture.Then, solid mixture is ground to form
Powder（Device is Achatess beveller）；
2nd, the mixture pyrolysis of iron porphyrin and Calcium Carbonate are generated into diamond and graphene microchip
Next, resulting mix powder is put in tube furnace, in nitrogen atmosphere, pressure is that a standard is big
Air pressure, is heated to 1000 degrees Celsius and is incubated five hours.
3rd, thermal decomposition product is processed, obtains product
It is after heating terminates, to be cooled to room temperature, mixture is flowed back 20 hours in concentrated hydrochloric acid（Device is flask add-back stream
Condensing tube）.After backflow terminates, room temperature is cooled to, centrifugation takes solid, and deionized water is washed till neutrality.It is then centrifuged for
Separation takes solid, and resulting solid is flowed back in perchloric acid, and in bottle, black disappears.After backflow terminates, it is cooled to
Room temperature, centrifugation take solid, and deionized water is washed till neutrality and dries（Device is centrifuge and baking oven）.Product is Buddha's warrior attendant
Stone.
Embodiment 3：
The method for preparing diamond of the present embodiment, comprises the following steps：
1st, by Vitamin B12 and Calcium Carbonate mix homogeneously
Vitamin B12（1 gram）It is dissolved in 150 milliliters of water（Device is beaker）, it is subsequently adding Calcium Carbonate（0.1 gram）Stirring is equal
It is even（Device is magnetic stirring apparatuss）, then water is evaporated obtains solid mixture.Then, by solid mixture grind into powder（Dress
It is set to Achatess beveller）；
2nd, the mixture pyrolysis of Vitamin B12 and Calcium Carbonate are generated into diamond and graphene microchip
Next, resulting mix powder is put in tube furnace, in nitrogen atmosphere, pressure is that a standard is big
Air pressure, is heated to 1000 degrees Celsius and is incubated two hours.
3rd, thermal decomposition product is processed, obtains product
It is after heating terminates, to be cooled to room temperature, mixture is flowed back 20 hours in concentrated hydrochloric acid（Device is flask add-back stream
Condensing tube）.After backflow terminates, room temperature is cooled to, centrifugation takes solid, and deionized water is washed till neutrality.It is then centrifuged for
Separation takes solid, and resulting solid is flowed back in perchloric acid, and in bottle, black disappears.After backflow terminates, it is cooled to
Room temperature, centrifugation take solid, and deionized water is washed till neutrality and dries（Device is centrifuge and baking oven）.Product is Buddha's warrior attendant
Stone.
Embodiment 4
The method for preparing diamond of the present embodiment, comprises the following steps：
1st, by temple construction and Calcium Carbonate mix homogeneously；
Temple construction（10 grams）It is dissolved in 250 milliliters of water（Device is beaker）, it is subsequently adding Calcium Carbonate（10 grams）Stir
Mix uniform（Device is magnetic stirring apparatuss）, then water is evaporated obtains solid mixture.Then, by solid mixture grind into powder
（Device is Achatess beveller）；
2nd, the mixture pyrolysis of temple construction and Calcium Carbonate are generated into diamond and graphene microchip
Next, resulting mix powder is put in tube furnace, in nitrogen atmosphere, pressure is that a standard is big
Air pressure, is heated to 600 degrees Celsius and is incubated five hours.
3rd, thermal decomposition product is processed, obtains product
It is after heating terminates, to be cooled to room temperature, mixture is flowed back 20 hours in concentrated hydrochloric acid（Device is flask add-back stream
Condensing tube）.After backflow terminates, room temperature is cooled to, centrifugation takes solid, and deionized water is washed till neutrality.It is then centrifuged for
Separation takes solid, and resulting solid is flowed back in perchloric acid, and in bottle, black disappears.After backflow terminates, it is cooled to
Room temperature, centrifugation take solid, and deionized water is washed till neutrality and dries（Device is centrifuge and baking oven）.Product is Buddha's warrior attendant
Stone.
Embodiment 5
The method for preparing diamond of the present embodiment, comprises the following steps：
1st, by binuclear cluster complexes, temple construction and Calcium Carbonate mix homogeneously
Binuclear cluster complexes（1 gram）, temple construction（1 gram）It is dissolved in 250 milliliters of water（Device is beaker）, then
Add Calcium Carbonate（10 grams）Stir（Device is magnetic stirring apparatuss）, then water is evaporated obtains solid mixture.Then, will be solid
Body mixture grind into powder（Device is Achatess beveller）；
2nd, the mixture pyrolysis of binuclear cluster complexes, temple construction and Calcium Carbonate are generated into diamond and Graphene
Microplate
Next, resulting mix powder is put in tube furnace, in nitrogen atmosphere, pressure is that a standard is big
Air pressure, is heated to 700 degrees Celsius and is incubated five hours.
3rd, thermal decomposition product is processed, obtains product.
It is after heating terminates, to be cooled to room temperature, mixture is flowed back 20 hours in concentrated hydrochloric acid（Device is flask add-back stream
Condensing tube）.After backflow terminates, room temperature is cooled to, centrifugation takes solid, and deionized water is washed till neutrality.It is then centrifuged for
Separation takes solid, and resulting solid is flowed back in perchloric acid, and in bottle, black disappears.After backflow terminates, it is cooled to
Room temperature, centrifugation take solid, and deionized water is washed till neutrality and dries（Device is centrifuge and baking oven）.Product is Buddha's warrior attendant
Stone.
Embodiment 6
The method for preparing diamond of the present embodiment, comprises the following steps：
1st, perylene is modified Anderson type polyoxometallate and Calcium Carbonate mix homogeneously
The Anderson type polyoxometallate organic compound of perylene modification（1 gram）It is dissolved in 250 milliliters of water（Device is burning
Cup）, it is subsequently adding Calcium Carbonate（10 grams）Stir（Device is magnetic stirring apparatuss）, then water is evaporated obtains solid mixture.
Then, by solid mixture grind into powder（Device is Achatess beveller）；
2nd, the mixture pyrolysis of the Anderson type polyoxometallate and Calcium Carbonate of perylene modification are generated into diamond and graphite
Alkene microplate
Next, resulting mix powder is put in tube furnace, in nitrogen atmosphere, pressure is that a standard is big
Air pressure, is heated to 700 degrees Celsius and is incubated five hours.
3rd, thermal decomposition product is processed, obtains product.
It is after heating terminates, to be cooled to room temperature, mixture is flowed back 20 hours in concentrated hydrochloric acid（Device is flask add-back stream
Condensing tube）.After backflow terminates, room temperature is cooled to, centrifugation takes solid, and deionized water is washed till neutrality.It is then centrifuged for
Separation takes solid, and resulting solid is flowed back in perchloric acid, and in bottle, black disappears.After backflow terminates, it is cooled to
Room temperature, centrifugation take solid, and deionized water is washed till neutrality and dries（Device is centrifuge and baking oven）.Product is Buddha's warrior attendant
Stone.
The main innovation point of technical solution of the present invention：
1. the present invention adopts metallo-organic compound or coordination compound as carbon source and the catalysis of artificially synthesizing diamond
Agent, metallo-organic compound or coordination compound can regard the intermediate complex of carbon and catalyst as, can substantially reduce Buddha's warrior attendant
The temperature and pressure of the synthesis of stone.And the traditional method of diamond synthesis adopts graphite and metallic catalyst, carbon source and catalyst
Contact area less, needs very high temperature and pressure that reaction can just carried out.
2. the present invention first generates graphene microchip in the building-up process of diamond, is maintained using the Graphene of high intensity
Pressure inside reaction system, thus do not need extra pressurizer.And diamond synthesis traditional method adopts engine driven supercharging,
Equipment investment and equipment attrition are larger.
Technical solution of the present invention compares the Advantageous that have the advantage that or can reach with existing like product or method
Effect：
1. the relatively high temperature and high pressure method and explosion method diamond synthesis of industrial employing at present, of the invention to close under low-temp low-pressure
Into diamond（Can be 600 DEG C or so, the pressure of 0.1MPa）, the cost of investment and operating cost of equipment are reduced, are dropped significantly
The low production cost of diamond.
2. technical solution of the present invention, the diamond surface product of synthesis are big, and surface activity is high, is easily prepared into composite.
Claims (8)
1. a kind of synthetic method of diamond, it is characterised in that comprise the following steps：
1）, mixing
Metallo-organic compound and/or coordination compound are mixed with auxiliary agent；
2）, heating
To step 1）The mixture of gained is heated；
3）, isolate and purify
By step 2）The product for obtaining is placed in the solution of acidity and/or oxidisability and flows back, and removes graphene microchip and impurity, obtains
To diamond；
Step 2）In described heating process, heating and temperature control 400 DEG C to 1000 DEG C, Stress control 0.1 to
100MPa, heat time heating time 10 minutes to 10 hours；
Step 3）Described purification procedures are：By step 2）The product for obtaining is cooled to room temperature, is subsequently placed in concentrated hydrochloric acid
Backflow, is subsequently cooled to room temperature, and centrifugation takes solid, is washed till neutrality, then is centrifuged and takes solid, by the solid for obtaining
It is placed in perchloric acid and flows back, black disappears in bottle, after backflow terminates, be cooled to room temperature, centrifugation takes solid, is used in combination
Deionized water is washed till neutrality and dries, and obtains final product diamond.
2. according to a kind of synthetic method of the diamond described in claim 1, it is characterised in that step 1）Described in metal have
Machine compound is polyoxometallate organic compound, and described polyoxometallate is to be connected by oxygen by early transition metal ion
The class multi-metal oxygen cluster compound for connecing and being formed.
3. according to a kind of synthetic method of the diamond described in claim 1, it is characterised in that step 1）Described in auxiliary agent be carbon
Hydrochlorate, the carbonate include but is not limited to Li2CO3、Na2CO3、K2CO3、Rb2CO3、Cs2CO3、MgCO3、CaCO3、SrCO3、
BaCO3In one or more mixing.
4. according to a kind of synthetic method of the diamond described in claim 1, it is characterised in that step 1）Described in mixing
Cheng Zhong, is first dissolved in metallo-organic compound and/or coordination compound in solvent, is subsequently adding auxiliary agent, stir, then remove
Solvent is removed, solid mixture is obtained.
5. according to a kind of synthetic method of the diamond described in claim 4, it is characterised in that the solvent is water, ionic liquid
One or more mixing in body, organic solvent, supercritical fluid.
6. according to a kind of synthetic method of the diamond described in claim 1, it is characterised in that step 1）Described in metal have
Machine compound and/or coordination compound and the mass ratio of auxiliary agent are 1：N, wherein 0.1≤n≤10；Metallo-organic compound with match somebody with somebody
The mass ratio of position compound is 1：N, wherein 0.1≤n≤10.
7. according to a kind of synthetic method of the diamond described in claim 1, it is characterised in that step 2）Described heating process
In, protective gas need to be passed through into heater or heater is evacuated to into vacuum before heating.
8. according to a kind of synthetic method of the diamond described in claim 7, it is characterised in that the protective gas be nitrogen,
One or more mixing in helium, argon, neon, Krypton and xenon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510477824.2A CN104986762B (en) | 2015-08-05 | 2015-08-05 | Synthetizing method of diamonds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510477824.2A CN104986762B (en) | 2015-08-05 | 2015-08-05 | Synthetizing method of diamonds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104986762A CN104986762A (en) | 2015-10-21 |
| CN104986762B true CN104986762B (en) | 2017-04-12 |
Family
ID=54298692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510477824.2A Active CN104986762B (en) | 2015-08-05 | 2015-08-05 | Synthetizing method of diamonds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104986762B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776201B (en) * | 2016-04-07 | 2018-07-20 | 东南大学 | A kind of method of graphene oxide powder low-temp low-pressure synthesizing nano diamond |
| CN107601498B (en) * | 2017-10-31 | 2020-07-14 | 深圳市海明润超硬材料股份有限公司 | Purification method of diamond micro powder |
| CN109487251B (en) * | 2018-12-25 | 2020-07-07 | 兰州大学 | Preparation method of micro-nano diamond film |
| CN112899776A (en) * | 2021-01-19 | 2021-06-04 | 吉林大学 | Method for synthesizing boron-hydrogen co-doped diamond single crystal |
| CN116239111B (en) * | 2023-05-12 | 2023-08-01 | 北方工业大学 | Method for low-pressure synthesis of PDC powder precursor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8882872B2 (en) * | 2011-10-04 | 2014-11-11 | Baker Hughes Incorporated | Graphite coated metal nanoparticles for polycrystalline diamond compact synthesis |
-
2015
- 2015-08-05 CN CN201510477824.2A patent/CN104986762B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104986762A (en) | 2015-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105016331B (en) | Synthetic method of graphene microchip-diamond compound | |
| Han et al. | Hierarchical NiCo2O4 hollow nanocages for photoreduction of diluted CO2: Adsorption and active sites engineering | |
| CN104986762B (en) | Synthetizing method of diamonds | |
| Hong et al. | Precisely tunable thickness of graphitic carbon nitride nanosheets for visible-light-driven photocatalytic hydrogen evolution | |
| Joseph et al. | Borophene and boron fullerene materials in hydrogen storage: opportunities and challenges | |
| Wang et al. | Low-temperature plasma exfoliated n-doped graphene for symmetrical electrode supercapacitors | |
| Qiu et al. | Defect-rich activated carbons as active and stable metal-free catalyst for acetylene hydrochlorination | |
| CN102115069B (en) | Graphene with porous structure and preparation method of graphene | |
| Liu et al. | Understanding the role of few-layer graphene nanosheets in enhancing the hydrogen sorption kinetics of magnesium hydride | |
| Yeh et al. | Single-step growth of graphene and graphene-based nanostructures by plasma-enhanced chemical vapor deposition | |
| Chen et al. | Preparation and electrochemical hydrogen storage of boron nitride nanotubes | |
| Liu et al. | Controlling and formation mechanism of oxygen-containing groups on graphite oxide | |
| Zhang et al. | Preparation and desalination performance of multiwall carbon nanotubes | |
| Yang et al. | Boron nitride supported Ni nanoparticles as catalysts for hydrogen generation from hydrolysis of ammonia borane | |
| Su et al. | A simple method for preparing graphene nano-sheets at low temperature | |
| EP3085666B1 (en) | Method for repairing reduced graphene oxide | |
| Wu et al. | Ultrathin 2D metal–organic framework nanosheets prepared via sonication exfoliation of membranes from interfacial growth and exhibition of enhanced catalytic activity by their gold nanocomposites | |
| Ashok Kumar et al. | A review on graphene and its derivatives as the forerunner of the two-dimensional material family for the future | |
| Yu et al. | Enhanced nonradical catalytic oxidation by encapsulating cobalt into nitrogen doped graphene: highlight on interfacial interactions | |
| Wang et al. | Magnetic carbon nanotubes: Carbide nucleated electrochemical growth of ferromagnetic CNTs from CO2 | |
| Kuang et al. | Dehydrogenation of ammonia borane catalyzed by pristine and defective h-BN sheets | |
| KR20130079144A (en) | Graphene carbon-nanotube composite and spray pyrolysis process for preparing same | |
| Ashoka et al. | Nanostructural zinc oxide hollow spheres: A facile synthesis and catalytic properties | |
| Hu et al. | Copper induced hollow carbon nanospheres by arc discharge method: controlled synthesis and formation mechanism | |
| Wang et al. | Controllable synthesis of graphitic carbon nanostructures from ion-exchange resin-iron complex via solid-state pyrolysis process |
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 |