CN102796999A - Method for preparing two-dimensional self-supporting ultrathin transition metal sheets - Google Patents
Method for preparing two-dimensional self-supporting ultrathin transition metal sheets Download PDFInfo
- Publication number
- CN102796999A CN102796999A CN2012102735164A CN201210273516A CN102796999A CN 102796999 A CN102796999 A CN 102796999A CN 2012102735164 A CN2012102735164 A CN 2012102735164A CN 201210273516 A CN201210273516 A CN 201210273516A CN 102796999 A CN102796999 A CN 102796999A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- supporting
- organic amine
- ultrathin section
- preparation
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing two-dimensional self-supporting ultrathin transition metal sheets, relating to a method for preparing ultrathin transition metal sheets. The invention is designed for solving the problem of complicated process existing in the existing method for preparing two-dimensional self-supporting ultrathin transition metal sheets. The method comprises the following steps of: 1, preparing a non-polar organic solution of organic amine complexes containing metal ions; 2, carrying out reduction on the metal ions in the organic amine complexes containing metal ions so as to obtain black powder; and 3, carrying out high-temperature roasting on the black powder obtained in the step 2 so as to obtain a two-dimensional self-supporting ultrathin sheet subjected to heat treatment. A two-dimensional self-supporting ultrathin transition metal sheet prepared by using the method disclosed by the invention does not need to use a hard template, so that an operation of template removal is not required to be performed in follow-up treatment, therefore, the process is relatively simple, the cost is low, and the prepared two-dimensional self-supporting ultrathin transition metal sheet has good magnetic properties. The method disclosed by the invention is applied to the preparation field of ultrathin transition metal sheets.
Description
Technical field
The present invention relates to the preparation method of transition metal ultrathin section.
Background technology
The two-dimensional nano material for example Graphene etc. because of its unique physics, chemical property and application prospects people's attention extremely.The metallic sulfide of two dimension super-thin sheet-shaped has high energy/electron storage specific volume; The ultrathin section that discoveries such as H.Welle are assembled into by nano unit not only can keep the unitary Quantum Properties of zero-dimension nano, and owing to the stretching, extension at two-dimensional space makes the ultrathin section layer material have excellent mechanical property and electron transport ability concurrently.At present; The preparation method is single for the two dimension layer material; Mainly be to be that physics, electroless plating or crystal growth preparation are passed through in substrate with smooth solid phase template, the two-dimentional ultrathin section layer material that desire obtains self-supporting need pass through the loaded down with trivial details template procedure that goes, thereby has restricted the application of two-dimensional slices material.
The transition metal of nano-scale (iron, cobalt, nickel) material has good chemistry and physicals, in fields such as catalysis, electronics, magnetics good application prospects is arranged.Yet; Because the characteristic of transition metal (iron, cobalt, nickel) self structure characteristics and easy oxidation; Mostly the nano material of the transition metal of having reported at present (iron, cobalt, nickel) is to have the nanoparticle of tensio-active agent protection, and wherein mostly nanometer sheet is the hard template preparation, need slough template but will obtain separately the nano flake of self-supporting; Method technology is loaded down with trivial details, and is that two-dimentional self-supporting transition metal (iron, cobalt, the nickel) ultrathin section of guiding preparation does not appear in the newspapers yet with the interface.
Summary of the invention
The objective of the invention is to have the loaded down with trivial details problem of technology, thereby a kind of preparation method of two-dimentional self-supporting transition metal ultrathin section is provided in order to solve among the existing two-dimentional self-supporting transition metal ultrathin section preparation method.
A kind of preparation method of two-dimentional self-supporting transition metal ultrathin section realizes according to the following steps among the present invention:
One, transition metal inorganic salt and water are hybridly prepared into the inorganic salt solution that volumetric molar concentration is 0.001 ~ 0.1mol/L; Organic amine and alcohol are hybridly prepared into the organic amine alcoholic solution that concentration is 0.0025 ~ 0.25mol/L; Inorganic salt solution and organic amine alcoholic solution are mixed, and the mol ratio that makes transition metal inorganic salt and organic amine is 1:1.5 ~ 8, at 25 ℃, stirring velocity is to stir 0.5 ~ 10min under the condition of 100 ~ 1000r/min; Obtain containing the muddy liquid of the organic amine title complex of metals ion; In muddy liquid, add non-polar organic solvent, low whipping speed is to stir 0.5 ~ 10min under 300 ~ 800r/min condition, leave standstill 5 ~ 15min after; The organic amine title complex non-polar organic solutions of the metals ion that obtains is transferred to organic phase in the airtight reflux;
Two, under protection of inert gas; At 15 ~ 99 ℃, stirring velocity is stirring and refluxing 15min under 300 ~ 800r/min condition; Adding concentration in the reaction system of rate of addition after refluxing with 20 ~ 100mL/h is 0.001 ~ 0.1mol/L Peng Qinghuana frozen water solution; Making the mol ratio of the transition metal inorganic salt that add in Peng Qinghuana and the step 1 of adding is 5 ~ 15:1, drips continued reaction 0.5 ~ 2h, and reaction product is cooled to 25 ℃; Reaction product separated obtaining sample, the sample washing is placed on vacuum-drying 0.5 ~ 2h obtains black powder in 50 ℃ ~ 80 ℃ vacuum drying ovens;
Three, with step 2 gained black powder under the protection of inert gas condition in tube furnace calcination process, promptly obtain two-dimentional self-supporting transition metal ultrathin section;
Wherein the transition metal inorganic salt in the step 1 are inorganic molysite, inorganic cobalt salt or inorganic nickel; Said inorganic molysite is one or more a mixture of iron nitrate, Iron nitrate, iron(ic)chloride, iron protochloride, ferric sulfate and ferrous sulfate; The mixture of one or more that said inorganic cobalt salt is rose vitriol, Xiao Suangu, NSC 51149 and Cobaltous diacetate; Said inorganic nickel is one or more the mixture in nickelous nitrate, single nickel salt, nickel acetate and the nickelous chloride;
Organic amine in the step 1 is one or more the mixture in amino dodecane, tetradecy lamine, cetylamine and the stearylamine;
Alcohol is a kind of in methyl alcohol, ethanol and the propyl alcohol or several kinds mixture wherein in the step 1;
Non-polar organic solvent in the step 1 is one or more the mixture in toluene, normal butane, Skellysolve A, normal hexane, hexanaphthene, tetracol phenixin and the sherwood oil;
Rare gas element in the step 2 and three is the mixed gas of one or more gases in nitrogen, argon gas and the helium;
Peng Qinghuana frozen water solution in the step 2 is that temperature is 0 ℃ a sodium borohydride aqueous solution;
Separation in the step 2 is that in magnetic resolution, spinning and the suction filtration separation method one or more are used in combination;
Roasting condition is 1 ~ 10 ℃/min of temperature rise rate in the step 3,200 ~ 600 ℃ of maturing temperatures, inert atmosphere flow 20 ~ 1500mL/min, roasting time 5min ~ 10h.
Advantage of the present invention: one, the present invention utilizes water miscible strong reductant will contain transition metal (iron, cobalt, nickel) ionic organic amine title complex and is reduced into metal nanoparticle; And under the guide effect of interface, realize the nanoparticle assembling, thereby realized the preparation of two-dimentional self-supporting transition metal (iron, cobalt, nickel) ultrathin section; Two, the present invention has broken through the idea of traditional liquid-liquid interface reaction; In reaction process,, quicken interfacial mass transfer speed and speed of response, make a large amount of nanoparticles under the IT effect, be squeezed into the laminated structure of self-supporting through conditions such as heating, stirring, feeding rare gas elementes; Need not use hard template; Therefore subsequent disposal need not template, and technology is simple relatively, and cost is low; Three, the present invention is aspect preparation two-dimensional metallic thin slice, and compound method is novel, has certain universality; Prepared two-dimentional self-supporting transition metal (iron, cobalt, nickel) ultrathin section exists wide application prospect at aspects such as magnetic recording material, absorbing material, hydrogen reduction and catalysis.
Description of drawings
Fig. 1 is preceding 50000 times of sem photographs of self-supporting cobalt ultrathin section of calcination process that test one step 2 obtains;
Fig. 2 is preceding 15000 times of transmission electron microscope pictures of self-supporting cobalt ultrathin section of calcination process that test one step 2 obtains;
Fig. 3 is preceding 300000 times of transmission electron microscope pictures of self-supporting cobalt ultrathin section of calcination process that test one step 2 obtains, and the illustration among Fig. 3 is preceding 800000 times of transmission electron microscope pictures of self-supporting cobalt ultrathin section of calcination process that test one step 2 obtains;
Fig. 4 is the energy spectrum analysis figure of the self-supporting cobalt ultrathin section before the calcination process that obtains of test one step 2;
Fig. 5 be self-supporting cobalt ultrathin section before the calcination process that obtains of test one step 2 at externally-applied magnetic field 2T, temperature is the back-shaped curve of magnetic hysteresis that 300K measures down;
Fig. 6 is test one step 3 40000 times of sem photographs of self-supporting cobalt ultrathin section after 500 ℃ of calcination process;
Fig. 7 is the X-ray diffraction spectrogram of the self-supporting cobalt ultrathin section that obtains; Fig. 7 is an X-ray diffraction spectrum of testing the self-supporting cobalt ultrathin section that obtains before the calcination process in the step 2 a); Fig. 7 b) be the X-ray diffraction spectrum of the self-supporting cobalt ultrathin section after 500 ℃ of calcination process in test one step 3, Fig. 7 c) be the X-ray diffraction spectrum of the self-supporting cobalt ultrathin section after 700 ℃ of calcination process in test four step 3;
Fig. 8 tests the self-supporting cobalt ultrathin section of a step 3 after 500 ℃ of calcination process at externally-applied magnetic field 2T, and temperature is that 300K measures the back-shaped curve of magnetic hysteresis down;
Fig. 9 is the 25000 times of transmission electron microscope pictures of self-supporting iron ultrathin section that obtain before the test two step 2 calcination process;
Figure 10 is the 15000 times of transmission electron microscope pictures of self-supporting nickel ultrathin section that obtain before the test three step 2 calcination process.
Embodiment
Embodiment one: a kind of preparation method of two-dimentional self-supporting transition metal ultrathin section is realized by following step among the present invention:
One, transition metal inorganic salt and water are hybridly prepared into the inorganic salt solution that volumetric molar concentration is 0.001 ~ 0.1mol/L; Organic amine and alcohol are hybridly prepared into the organic amine alcoholic solution that concentration is 0.0025 ~ 0.25mol/L; Inorganic salt solution and organic amine alcoholic solution are mixed, and the mol ratio that makes transition metal inorganic salt and organic amine is 1:1.5 ~ 8, at 25 ℃, stirring velocity is to stir 0.5 ~ 10min under the condition of 100 ~ 1000r/min; Obtain containing the muddy liquid of the organic amine title complex of metals ion; In muddy liquid, add non-polar organic solvent, low whipping speed is to stir 0.5 ~ 10min under 300 ~ 800r/min condition, leave standstill 5 ~ 15min after; The organic amine title complex non-polar organic solutions of the metals ion that obtains is transferred to organic phase in the airtight reflux;
Two, under protection of inert gas; At 15 ~ 99 ℃, stirring velocity is stirring and refluxing 15min under 300 ~ 800r/min condition; Adding concentration in the reaction system of rate of addition after refluxing with 20 ~ 100mL/h is 0.001 ~ 0.1mol/L Peng Qinghuana frozen water solution; Making the mol ratio of the transition metal inorganic salt that add in Peng Qinghuana and the step 1 of adding is 5 ~ 15:1, drips continued reaction 0.5 ~ 2h, and reaction product is cooled to 25 ℃; Reaction product separated obtaining sample, the sample washing is placed on vacuum-drying 0.5 ~ 2h obtains black powder in 50 ℃ ~ 80 ℃ vacuum drying ovens;
Three, with step 2 gained black powder under the protection of inert gas condition at the tubular type kiln roasting, promptly obtain two-dimentional self-supporting transition metal ultrathin section;
Wherein the transition metal inorganic salt in the step 1 are inorganic molysite, inorganic cobalt salt or inorganic nickel; Said inorganic molysite is one or more a mixture of iron nitrate, Iron nitrate, iron(ic)chloride, iron protochloride, ferric sulfate and ferrous sulfate; The mixture of one or more that said inorganic cobalt salt is rose vitriol, Xiao Suangu, NSC 51149 and Cobaltous diacetate; Said inorganic nickel is one or more the mixture in nickelous nitrate, single nickel salt, nickel acetate and the nickelous chloride;
Organic amine in the step 1 is one or more the mixture in amino dodecane, tetradecy lamine, cetylamine and the stearylamine;
Alcohol is a kind of in methyl alcohol, ethanol and the propyl alcohol or several kinds mixture wherein in the step 1;
Non-polar organic solvent in the step 1 is one or more the mixture in toluene, normal butane, Skellysolve A, normal hexane, hexanaphthene, tetracol phenixin and the sherwood oil;
Rare gas element in the step 2 and three is the mixed gas of one or more gases in nitrogen, argon gas and the helium;
Peng Qinghuana frozen water solution in the step 2 is that temperature is 0 ℃ a sodium borohydride aqueous solution;
Separation in the step 2 is that in magnetic resolution, spinning and the suction filtration separation method one or more are used in combination;
Roasting condition is 1 ~ 10 ℃/min of temperature rise rate in the step 3,200 ~ 600 ℃ of maturing temperatures, inert atmosphere flow 20 ~ 1500mL/min, roasting time 5min ~ 10h.
When inorganic molysite is mixture in this embodiment step 1, presses arbitrary proportion between each component and mix;
When inorganic cobalt salt is mixture in this embodiment step 1, presses arbitrary proportion between each component and mix;
When inorganic nickel is mixture in this embodiment step 1, presses arbitrary proportion between each component and mix;
When the organic amine in this embodiment step 1 is mixture, presses arbitrary proportion between each component and mix;
When alcohol is mixture in this embodiment step 1, presses arbitrary proportion between each component and mix;
When the non-polar organic solvent in this embodiment step 1 is mixture, presses arbitrary proportion between each component and mix;
When the rare gas element in this embodiment step 2 and three is mixture, presses arbitrary proportion between each component and mix.
Advantage of the present invention: one, the present invention utilizes water miscible strong reductant will contain transition metal (iron, cobalt, nickel) ionic organic amine title complex and is reduced into metal nanoparticle; And under the guide effect of interface, realize the nanoparticle assembling, thereby realized the preparation of two-dimentional self-supporting transition metal (iron, cobalt, nickel) ultrathin section; Two, the present invention has broken through the idea of traditional liquid-liquid interface reaction; In reaction process,, quicken interfacial mass transfer speed and speed of response, make a large amount of nanoparticles under the IT effect, be squeezed into the laminated structure of self-supporting through conditions such as heating, stirring, feeding rare gas elementes; Need not use hard template; Therefore subsequent disposal need not template, and technology is simple relatively, and cost is low; Three, the present invention is aspect preparation two-dimensional metallic thin slice, and compound method is novel, has certain universality; Prepared two-dimentional self-supporting transition metal (iron, cobalt, nickel) ultrathin section, and exist wide application prospect at aspects such as magnetic recording material, absorbing material, hydrogen reduction and catalysis.
Embodiment two: what this embodiment and embodiment one were different is: in the step 1 transition metal inorganic salt are mixed with the solution that volumetric molar concentration is 0.01 ~ 0.05mol/L.Other step and parameter are identical with embodiment one.
Embodiment three: what this embodiment was different with embodiment one or two is: the mol ratio of transition metal inorganic salt and organic amine is 1:3.5 ~ 6 in the step 1.Other step and parameter are identical with embodiment one or two.
Embodiment four: what this embodiment was different with one of embodiment one to three is: the mol ratio of transition metal inorganic salt and organic amine is 1:5 in the step 1.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: what this embodiment was different with one of embodiment one to four is: in the step 1 organic amine and alcohol are hybridly prepared into the organic amine alcoholic solution that concentration is 0.05 ~ 0.15mol/L.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: what this embodiment was different with one of embodiment one to five is: in the step 1 organic amine and alcohol are hybridly prepared into the organic amine alcoholic solution that concentration is 0.10mol/L.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: what this embodiment was different with one of embodiment one to six is: adding concentration in the reaction system of rate of addition after refluxing with 40 ~ 80mL/h in the step 2 is 0.01 ~ 0.05mol/L Peng Qinghuana frozen water solution.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: what this embodiment was different with one of embodiment one to seven is: adding concentration in the reaction system of rate of addition after refluxing with 60mL/h in the step 2 is 0.03mol/L Peng Qinghuana frozen water solution.Other step and parameter are identical with one of embodiment one to seven.
Embodiment nine: what this embodiment was different with one of embodiment one to eight is: the roasting condition in the step 3 is 3 ~ 7 ℃/min of temperature rise rate, 300 ~ 500 ℃ of maturing temperatures, inert atmosphere flow 50 ~ 1000mL/min, roasting time 2 ~ 8h.Other step and parameter are identical with one of embodiment one to eight.
Embodiment ten: what this embodiment was different with one of embodiment one to nine is: the roasting condition in the step 3 is 5 ℃/min of temperature rise rate, 400 ℃ of maturing temperatures, inert atmosphere flow 800mL/min, roasting time 5h.Other step and parameter are identical with one of embodiment one to nine.
Adopt following verification experimental verification invention effect:
Test one: a kind of preparation method of two-dimentional self-supporting transition metals cobalt ultrathin section, specifically accomplish according to the following steps:
One, the preparation of cobalt ion organic amine title complex: Xiao Suangu joined in the zero(ppm) water dissolve, be mixed with the cobalt nitrate solution that the cobalt ion volumetric molar concentration is 0.001mol/L; In 25 ℃ of room temperatures, stirring velocity is under the 300r/min condition; In the aqueous solution of the above-mentioned Xiao Suangu of 50mL, adding isopyknic volumetric molar concentration is the ethanolic soln of 0.005mol/L oleyl amine; Stir, mix 3min, obtain containing cobalt metal ionic organic amine title complex; In the organic amine title complex of cobalt ion, add 50mL toluene; Stir 5min; Leave standstill the 15min layering; And the organic phase toluene layer is separated the oleyl amine title complex of the cobalt ion that obtains being dissolved in the toluene with separating funnel, and transfer in the sealing reflux, obtain being dissolved in the oleyl amine title complex of the cobalt ion in the toluene;
Two, reduction: nitrogen atmosphere protection is heated to 45 ℃ with the oleyl amine title complex of step 1 gained down, low whipping speed be stir under the 300r/min condition, backflow 15min; Continuing heated and stirred refluxes; Be that the Peng Qinghuana frozen water solution of 0.02mol/L dropwise adds with 20mL concentration simultaneously with the rate of addition of 50mL/h; After adding reaction 2h, be cooled to 25 ℃ of room temperatures and magnetic resolution and obtain black powder shape product, water, ethanol alternately wash 5 times; At 50 ℃ of following vacuum drying 2h, promptly get two-dimentional self-supporting cobalt ultrathin section;
Three, high-temperature roasting: at the nitrogen atmosphere flow is under the condition of 600mL/min; Heat-up rate with 10 ℃/min rises to 500 ℃ by 25 ℃ of room temperatures; The two-dimentional self-supporting cobalt ultrathin section 2h of preparation in the heat treatment step two promptly gets the two-dimentional self-supporting cobalt ultrathin section after the thermal treatment;
The mol ratio of organic amine and cobalt salt is 1:5 in this testing sequence one;
Alcoholic solvent is 1:1 with the volume ratio that adds entry in this testing sequence one;
Non-polar organic solvent is 1:1 with the volume ratio that adds entry in this testing sequence one;
The mol ratio of the cobalt ion that Peng Qinghuana that adds in this testing sequence two and step 1 add is 1:8.
The two-dimentional self-supporting cobalt ultrathin section that obtains in this testing sequence two is carried out the pattern test:
Fig. 1 is that step 2 obtains the preceding 50000 times of sem photographs of two-dimentional self-supporting cobalt ultrathin section of calcination process in the test one, can be known that by Fig. 1 the microscopic appearance of product is a two-dimensional layered structure, and lamella is thinner, and the lamella size is single, has dispersity preferably;
Fig. 2 is 15000 times of transmission electron microscope pictures of two-dimentional self-supporting cobalt ultrathin section before the calcination process that step 2 obtains in the test one, can be known that by Fig. 2 sample is the two-dimensional sheet structure, and lamella is approximately several microns, goes out to estimate thickness from fold and is about 2nm;
Fig. 3 is 300000 times of transmission electron microscope pictures of two-dimentional self-supporting cobalt ultrathin section before the calcination process that step 2 obtains in the test one, can be known by Fig. 3, and two-dimentional self-supporting cobalt ultrathin section is piled up by the nanometer small-particle and formed, and has nano level hole; Fig. 3 illustration is 800000 times of transmission electron microscope pictures of two-dimentional self-supporting cobalt ultrathin section before the calcination process that obtains of step 2, can be known that by Fig. 3 illustration spacing of lattice d=0.216nm is the spacing of Co (100) crystal face, and spacing of lattice d=0.41nm is CoCo
2O3The spacing of crystal face, this is because the cobalt ultrathin section for preparing is more active, is exposed to that surface portion is oxidized to CoCo in the air
2O
3
Fig. 4 is that two-dimentional self-supporting cobalt ultrathin section carries out energy spectrum analysis figure before the calcination process that step 2 obtains in a pair of test of test, and can be known that by Fig. 4 sample is made up of cobalt, oxygen, carbon, wherein Wt (%): carbon is 1.31; Oxygen 8.11, cobalt 90.58, At (%): carbon is 5.07; Oxygen 23.55, cobalt 71.39, the content of oxygen, carbon is very low; This is because the cobalt sheet is exposed in the air, makes the surface form the fine and close sull of one deck, and the inside of lamella still exists with the form of cobalt simple substance;
Fig. 5 is to testing the test pattern that two-dimentional self-supporting cobalt ultrathin section before the calcination process that step 2 obtains in has carried out the back-shaped curve of magnetic hysteresis; Can know by Fig. 5; The B-H loop of the back-shaped curve of magnetic hysteresis is a closed hoop; Explanation two-dimentional self-supporting cobalt ultrathin section under 300K has superparamagnetism, and good magnetic performance is arranged;
Fig. 6 is that the two-dimentional self-supporting cobalt ultrathin section after the step 3 thermal treatment carries out 40000 times of electron-microscope scanning figure in one to testing, and by 6 knowledges, sheet structure remains unchanged basically after 500 ℃ thermal treatment, but spherical reunion occurred;
Two-dimentional self-supporting cobalt ultrathin section to testing thermal treatment front and back has carried out the X-ray diffraction spectroscopic analysis:
Fig. 7 is the X-ray diffraction spectrum of step 2 without the two-dimentional self-supporting cobalt ultrathin section sample of bakingout process a), can know that by figure sample does not have the X-ray diffraction peak, is that percent crystallinity is not high because sample is to be made up of the crystallite particle, and lamella is thin to be caused;
Fig. 7 b) is the X-ray diffraction spectrum of the two-dimentional self-supporting cobalt ultrathin section sample of step 3 after through 500 ℃ of thermal treatments; From figure, can see the diffraction peak of cobalt simple substance; While shows that with the X-ray diffraction peak of the oxide compound of cobalt thermal treatment has improved the percent crystallinity of cobalt ultrathin section;
Fig. 8 is to testing the test pattern that the two-dimentional self-supporting cobalt ultrathin section after the step 3 thermal treatment in has carried out the back-shaped curve of magnetic hysteresis; Can know by figure; The back-shaped curve of magnetic hysteresis has tangible B-H loop; Explain through 500 ℃ of heat treated two-dimentional self-supporting cobalt ultrathin sections under 300K, to show ferromegnetism, show that heat treatment process can regulate and control the magnetic performance of ultra-thin lamella.
Test two: a kind of preparation method of two-dimentional self-supporting transition metal iron ultrathin section, specifically accomplish according to the following steps:
One, the preparation of iron ion organic amine title complex: iron(ic)chloride joined in the zero(ppm) water dissolve, be mixed with the ferric chloride Solution(38 that the iron ion volumetric molar concentration is 0.001mol/L; 25 ℃ of room temperatures, under the stirring velocity 300r/min condition, in the aqueous solution of above-mentioned 50mL iron(ic)chloride, adding isopyknic concentration is the ethanolic soln of 0.0035mol/L oleyl amine, stirs 3min, obtains containing the organic amine title complex of iron ion; In the organic amine title complex of iron ion, add 50mL toluene, stir 5min, leave standstill the 15min layering, and with separating funnel organic phase is separated and to be transferred in the sealing reflux, obtain being dissolved in iron ion in the toluene the oleyl amine title complex;
Two, reduction: the nitrogen atmosphere protection down; The oleyl amine title complex of step 1 gained is heated to 65 ℃, and low whipping speed is stirring, backflow 15min under the 300r/min condition, continues heating, stirs, refluxes; Be that the Peng Qinghuana frozen water solution of 0.02mol/L dropwise adds with 20mL concentration simultaneously with the rate of addition of 50mL/h; Behind the reaction 2h, be cooled to 25 ℃ of room temperatures and magnetic resolution and obtain black powder shape product, water, ethanol alternately wash 5 times; At 50 ℃ of following vacuum drying 2h, promptly get two-dimentional self-supporting iron ultrathin section;
Three, high-temperature roasting: at the nitrogen atmosphere flow is under the 600mL/min condition; Heat-up rate with 10 ℃/min rises to 500 ℃ by 25 ℃ of room temperatures; The two-dimentional self-supporting iron ultrathin section 2h of preparation in the heat treatment step two promptly gets the two-dimentional self-supporting iron ultrathin section after the thermal treatment;
The mol ratio that adds organic amine and molysite in this testing sequence one is 1:3.5;
The volume ratio of alcoholic solvent and water is 1:1 in this testing sequence one;
The volume ratio of non-polar organic solvent and water is 1:1 in this testing sequence one;
The mol ratio that adds the iron ion of Peng Qinghuana and step 1 adding in this testing sequence two is 1:8.
The two-dimentional self-supporting iron ultrathin section that this testing sequence two is obtained carries out the pattern test:
Fig. 9 is the 25000 times of sem photographs of two-dimentional self-supporting iron ultrathin section that obtain before the step 2 calcination process in the test two, can know that by figure the microscopic appearance of product is a two-dimensional layered structure, and lamella is thinner, and the lamella size is single, has dispersity preferably.
Test three: a kind of preparation method of two-dimentional self-supporting transiting metal nickel ultrathin section, specifically accomplish according to the following steps:
One, the preparation of nickel ion organic amine title complex: nickelous chloride joined in the zero(ppm) water dissolve, be mixed with the nickel chloride solution that the nickel ion volumetric molar concentration is 0.001mol/L; Under 25 ℃ of room temperatures, under the stirring velocity 300r/min condition, in the aqueous solution of the nickelous chloride of above-mentioned 50mL, adding isopyknic volumetric molar concentration is the ethanolic soln of 0.0035mol/L oleyl amine, stirs 3min, obtains containing the organic amine title complex of metals ion nickel; In the organic amine title complex of nickel ion, add toluene, stir 5min, leave standstill the 15min layering, and with separating funnel organic phase is separated and to be transferred in the sealing reflux, obtain being dissolved in the oleyl amine title complex of the nickel ion in the toluene;
Two, reduction: nitrogen atmosphere protection is heated to 45 ℃ with the oleyl amine title complex of step 1 gained down, stirring velocity be stir under the 300r/min condition, backflow 15min; Continue heating, stir, reflux; Be that the Peng Qinghuana frozen water solution of 0.02mol/L dropwise adds with 20mL concentration simultaneously with the rate of addition of 50mL/h; Behind the reaction 2h, be cooled to 25 ℃ of room temperatures and magnetic resolution and obtain black powder shape product, water, ethanol alternately wash 5 times; At 50 ℃ of following vacuum drying 2h, promptly get two-dimentional self-supporting nickel ultrathin section;
Three, high-temperature roasting: at the nitrogen atmosphere flow is under the 600mL/min condition, rises to 500 ℃ with the heat-up rate of 10 ℃/min by room temperature, and the two-dimentional self-supporting nickel ultrathin section 2h of preparation in the heat treatment step two promptly gets the two-dimentional self-supporting nickel ultrathin section after the thermal treatment;
The mol ratio of organic amine and nickel salt is 1:3.5 in this testing sequence one;
The volume ratio of alcoholic solvent and water is 1:1 in this testing sequence one;
The volume ratio of non-polar organic solvent and water is 1:1 in this testing sequence one;
In this testing sequence two in Peng Qinghuana and the step 1 mol ratio of nickel ion be 1:8.
The two-dimentional self-supporting nickel ultrathin section that this testing sequence two is obtained carries out the pattern test:
Figure 10 is the 15000 times of sem photographs of two-dimentional self-supporting nickel ultrathin section that obtain before the step 2 calcination process in the test three; Can be known that by figure the microscopic appearance of product is a two-dimensional layered structure and with a little nanoparticle, lamella is thinner; The lamella size is single, has dispersity preferably.
Test four: a kind of preparation method of two-dimentional self-supporting transition metals cobalt ultrathin section, specifically accomplish according to the following steps:
One, the preparation of cobalt ion organic amine title complex: Xiao Suangu joined in the zero(ppm) water dissolve, be configured to the cobalt nitrate solution that the cobalt ion volumetric molar concentration is 0.001mol/L; Under 25 ℃ of room temperatures, stirring velocity 300r/min condition, in the aqueous solution of the above-mentioned Xiao Suangu of 50mL, adding isopyknic volumetric molar concentration is the ethanolic soln of 0.005mol/L oleyl amine, stirs, mixes 3min, obtains containing the organic amine title complex of cobalt ion; In the organic amine title complex of cobalt ion, add 50mL toluene; Stir 5min; Leave standstill the 15min layering; And with separating funnel the organic phase toluene layer is separated the oleyl amine title complex of the cobalt ion that obtains being dissolved in the toluene, after transfer in the sealing reflux, obtain being dissolved in cobalt ion in the toluene the oleyl amine title complex;
Two, reduction: nitrogen atmosphere protection is heated to 45 ℃ with the oleyl amine title complex of step 2 gained down, and stirring velocity 300r/min stirs, backflow 15min; Continuing heated and stirred refluxes; Be that the Peng Qinghuana frozen water solution of 0.02mol/L dropwise adds with 20mL concentration simultaneously with the rate of addition of 50mL/h; After reacting 2h afterwards, be cooled to 25 ℃ of room temperatures and magnetic resolution and obtain black powder shape product, water, ethanol alternately wash 5 times; At 50 ℃ of following vacuum drying 2h, promptly get two-dimentional self-supporting cobalt ultrathin section;
Three, high-temperature roasting: at the nitrogen atmosphere flow is under the 600mL/min condition, rises to 600 ℃ with the heat-up rate of 10 ℃/min by room temperature, and the two-dimentional self-supporting cobalt ultrathin section 2h of preparation in the heat treatment step two promptly gets the two-dimentional self-supporting cobalt ultrathin section after the thermal treatment.
The mol ratio of organic amine and cobalt salt is 1:5 in this testing sequence one;
Alcoholic solvent is 1:1 with the volume ratio that adds entry in this testing sequence one;
Non-polar organic solvent is 1:1 with the volume ratio that adds entry in this testing sequence one;
The mol ratio of the cobalt ion that Peng Qinghuana that this testing sequence two adds and step 1 add is 1:8.
Two-dimentional self-supporting cobalt ultrathin section to before and after this test thermal treatment has carried out the X-ray diffraction spectroscopic analysis; Fig. 7 c) is the X-ray diffraction spectrum of the two-dimentional self-supporting cobalt ultrathin section sample of step 3 after through 700 ℃ of thermal treatments; Can know by figure; See the diffraction peak of cobalt simple substance, the while shows that with the X-ray diffraction peak of the oxide compound of cobalt thermal treatment has improved the percent crystallinity of cobalt ultrathin section.
Claims (10)
1. the preparation method of a two-dimentional self-supporting transition metal ultrathin section is characterized in that the preparation method of two-dimentional self-supporting transition metal ultrathin section realizes according to the following steps:
One, transition metal inorganic salt and water are hybridly prepared into the inorganic salt solution that volumetric molar concentration is 0.001 ~ 0.1mol/L; Organic amine and alcohol are hybridly prepared into the organic amine alcoholic solution that concentration is 0.0025 ~ 0.25mol/L; Inorganic salt solution and organic amine alcoholic solution are mixed, and the mol ratio that makes transition metal inorganic salt and organic amine is 1:1.5 ~ 8, at 25 ℃, stirring velocity is to stir 0.5 ~ 10min under the condition of 100 ~ 1000r/min; Obtain containing the muddy liquid of the organic amine title complex of metals ion; In muddy liquid, add non-polar organic solvent, low whipping speed is to stir 0.5 ~ 10min under 300 ~ 800r/min condition, leave standstill 5 ~ 15min after; The organic amine title complex non-polar organic solutions of the metals ion that obtains is transferred to organic phase in the airtight reflux;
Two, under the protection of inert gas; At 15 ~ 99 ℃, stirring velocity is stirring and refluxing 15min under 300 ~ 800r/min condition; Adding concentration in the reaction system of rate of addition after refluxing with 20 ~ 100mL/h is 0.001 ~ 0.1mol/L Peng Qinghuana frozen water solution; Making the mol ratio of the transition metal inorganic salt that add in Peng Qinghuana and the step 1 of adding is 5 ~ 15:1, drips continued reaction 0.5 ~ 2h, and reaction product is cooled to 25 ℃; Reaction product separated obtaining sample, the sample washing is placed on vacuum-drying 0.5 ~ 2h obtains black powder in 50 ℃ ~ 80 ℃ vacuum drying ovens;
Three, with step 2 gained black powder under the protection of inert gas condition at the tubular type kiln roasting, promptly obtain two-dimentional self-supporting transition metal ultrathin section;
Wherein the transition metal inorganic salt in the step 1 are inorganic molysite, inorganic cobalt salt or inorganic nickel; Said inorganic molysite is one or more a mixture of iron nitrate, Iron nitrate, iron(ic)chloride, iron protochloride, ferric sulfate and ferrous sulfate; The mixture of one or more that said inorganic cobalt salt is rose vitriol, Xiao Suangu, NSC 51149 and Cobaltous diacetate; Said inorganic nickel is one or more the mixture in nickelous nitrate, single nickel salt, nickel acetate and the nickelous chloride;
Organic amine in the step 1 is one or more the mixture in amino dodecane, tetradecy lamine, cetylamine and the stearylamine;
Alcohol is a kind of in methyl alcohol, ethanol and the propyl alcohol or several kinds mixture wherein in the step 1;
Non-polar organic solvent in the step 1 is one or more the mixture in toluene, normal butane, Skellysolve A, normal hexane, hexanaphthene, tetracol phenixin and the sherwood oil;
Rare gas element in the step 2 and three is the mixed gas of one or more gases in nitrogen, argon gas and the helium;
Peng Qinghuana frozen water solution in the step 2 is that temperature is 0 ℃ a sodium borohydride aqueous solution;
Separation in the step 2 is that in magnetic resolution, spinning and the suction filtration separation method one or more are used in combination;
Roasting condition is 1 ~ 10 ℃/min of temperature rise rate in the step 3,200 ~ 600 ℃ of maturing temperatures, inert atmosphere flow 20 ~ 1500mL/min, roasting time 5min ~ 10h.
2. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 1 is characterized in that in the step 1 transition metal inorganic salt being mixed with the solution that volumetric molar concentration is 0.01 ~ 0.05mol/L.
3. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 1 and 2 is characterized in that the mol ratio of transition metal inorganic salt and organic amine is 1:3.5 ~ 6 in the step 1.
4. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 1 and 2 is characterized in that the mol ratio of transition metal inorganic salt and organic amine is 1:5 in the step 1.
5. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 3 is characterized in that in the step 1 organic amine and alcohol being hybridly prepared into the organic amine alcoholic solution that concentration is 0.05 ~ 0.15mol/L.
6. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 5 is characterized in that in the step 1 organic amine and alcohol being hybridly prepared into the organic amine alcoholic solution that concentration is 0.10mol/L.
7. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 6 is characterized in that adding concentration in the reaction system of rate of addition after refluxing with 40 ~ 80mL/h in the step 2 is 0.01 ~ 0.05mol/L Peng Qinghuana frozen water solution.
8. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 6 is characterized in that adding concentration in the reaction system of rate of addition after refluxing with 60mL/h in the step 2 is 0.03mol/L Peng Qinghuana frozen water solution.
9. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 7; It is characterized in that the roasting condition in the step 3 is 3 ~ 7 ℃/min of temperature rise rate; 300 ~ 500 ℃ of maturing temperatures, inert atmosphere flow 50 ~ 1000mL/min, roasting time 2 ~ 8h.
10. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 7 is characterized in that the roasting condition in the step 3 is 5 ℃/min of temperature rise rate, 400 ℃ of maturing temperatures, inert atmosphere flow 800mL/min, roasting time 5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210273516.4A CN102796999B (en) | 2012-08-02 | 2012-08-02 | Method for preparing two-dimensional self-supporting ultrathin transition metal sheets |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210273516.4A CN102796999B (en) | 2012-08-02 | 2012-08-02 | Method for preparing two-dimensional self-supporting ultrathin transition metal sheets |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102796999A true CN102796999A (en) | 2012-11-28 |
| CN102796999B CN102796999B (en) | 2014-04-16 |
Family
ID=47196290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210273516.4A Expired - Fee Related CN102796999B (en) | 2012-08-02 | 2012-08-02 | Method for preparing two-dimensional self-supporting ultrathin transition metal sheets |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102796999B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105033241A (en) * | 2015-06-04 | 2015-11-11 | 北京化工大学 | Ultrathin metallic nickel nanosheet, manufacturing method thereof and application of nanosheets as electrode materials |
| CN107398564A (en) * | 2017-07-25 | 2017-11-28 | 陕西师范大学 | A kind of preparation method of ultra-thin CoNi alloy nanos piece |
| AT518826A1 (en) * | 2016-07-11 | 2018-01-15 | Technische Universität Wien | Process for thermochemical energy storage |
| CN107915262A (en) * | 2017-11-08 | 2018-04-17 | 华东师范大学 | A kind of preparation method of two-dimensional ultrathin hydroxide |
| CN109417863A (en) * | 2016-04-22 | 2019-03-01 | 德雷塞尔大学 | Two-dimensional metallic carbide, nitride and carbon nitride films and compound for EMI shielding |
| CN111468151A (en) * | 2020-04-24 | 2020-07-31 | 宁夏大学 | Mo with lamellar structure2C cocatalyst, preparation and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3693618B2 (en) * | 2002-03-27 | 2005-09-07 | 和幸 田路 | Metal magnetic particles and method for producing the same |
| WO2009117718A1 (en) * | 2008-03-20 | 2009-09-24 | Northeastern University | Direct chemical synthesis of rare earth-transition metal alloy magnetic materials |
| CN101786169A (en) * | 2010-03-12 | 2010-07-28 | 江苏大学 | Controllable-appearance nickel nano film preparation method |
| WO2011057937A2 (en) * | 2009-11-16 | 2011-05-19 | Basf Se | Metal island coatings and method for synthesis |
| EP2411140A1 (en) * | 2009-03-24 | 2012-02-01 | Basf Se | Preparation of shaped metal particles and their uses |
| CN102560290A (en) * | 2010-12-24 | 2012-07-11 | 国家纳米技术与工程研究院 | Nano nickel boride (NiB) amorphous alloy and preparation method thereof |
-
2012
- 2012-08-02 CN CN201210273516.4A patent/CN102796999B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3693618B2 (en) * | 2002-03-27 | 2005-09-07 | 和幸 田路 | Metal magnetic particles and method for producing the same |
| WO2009117718A1 (en) * | 2008-03-20 | 2009-09-24 | Northeastern University | Direct chemical synthesis of rare earth-transition metal alloy magnetic materials |
| EP2411140A1 (en) * | 2009-03-24 | 2012-02-01 | Basf Se | Preparation of shaped metal particles and their uses |
| CN102365127A (en) * | 2009-03-24 | 2012-02-29 | 巴斯夫欧洲公司 | Preparation of shaped metal particles and their uses |
| WO2011057937A2 (en) * | 2009-11-16 | 2011-05-19 | Basf Se | Metal island coatings and method for synthesis |
| CN102712045A (en) * | 2009-11-16 | 2012-10-03 | 巴斯夫欧洲公司 | Metal island coatings and method for synthesis |
| CN101786169A (en) * | 2010-03-12 | 2010-07-28 | 江苏大学 | Controllable-appearance nickel nano film preparation method |
| CN102560290A (en) * | 2010-12-24 | 2012-07-11 | 国家纳米技术与工程研究院 | Nano nickel boride (NiB) amorphous alloy and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JUN YANG, EDWARD H. SARGENT, SHANA O. KELLEY, ET. AL.,: "A general phase-transfer protocol for metal ions and its application in nanocrystal synthesis", 《NATURE MATERIALS》, vol. 8, 31 August 2009 (2009-08-31), pages 683 - 689, XP055034006, DOI: 10.1038/nmat2490 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105033241A (en) * | 2015-06-04 | 2015-11-11 | 北京化工大学 | Ultrathin metallic nickel nanosheet, manufacturing method thereof and application of nanosheets as electrode materials |
| CN105033241B (en) * | 2015-06-04 | 2017-11-21 | 北京化工大学 | A kind of super thin metal nickel nano film, its preparation method and the application as electrode material |
| CN109417863A (en) * | 2016-04-22 | 2019-03-01 | 德雷塞尔大学 | Two-dimensional metallic carbide, nitride and carbon nitride films and compound for EMI shielding |
| AT518826A1 (en) * | 2016-07-11 | 2018-01-15 | Technische Universität Wien | Process for thermochemical energy storage |
| AT518826B1 (en) * | 2016-07-11 | 2018-09-15 | Univ Wien Tech | Process for thermochemical energy storage |
| CN107398564A (en) * | 2017-07-25 | 2017-11-28 | 陕西师范大学 | A kind of preparation method of ultra-thin CoNi alloy nanos piece |
| CN107915262A (en) * | 2017-11-08 | 2018-04-17 | 华东师范大学 | A kind of preparation method of two-dimensional ultrathin hydroxide |
| CN111468151A (en) * | 2020-04-24 | 2020-07-31 | 宁夏大学 | Mo with lamellar structure2C cocatalyst, preparation and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102796999B (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102796999B (en) | Method for preparing two-dimensional self-supporting ultrathin transition metal sheets | |
| Sun et al. | Simple synthesis of CuFe2O4 nanoparticles as gas-sensing materials | |
| Salavati-Niasari et al. | Synthesis of nickel and nickel oxide nanoparticles via heat-treatment of simple octanoate precursor | |
| Davar et al. | Thermal decomposition route for synthesis of Mn3O4 nanoparticles in presence of a novel precursor | |
| Zhai et al. | Ordered magnetic core–manganese oxide shell nanostructures and their application in water treatment | |
| Sivakumar et al. | Synthesis and characterization of NiFe2O4 nanosheet via polymer assisted co-precipitation method | |
| Beshkar et al. | Simple morphology-controlled fabrication of nickel chromite nanostructures via a novel route | |
| He et al. | Size and shape effects on magnetic properties of Ni nanoparticles | |
| Popkov et al. | Synthesis of phase-pure superparamagnetic nanoparticles of ZnFe2O4 via thermal decomposition of zinc-iron layered double hydroxysulphate | |
| CN106430327B (en) | A kind of porous sea urchin shape Fe3O4@C composites and preparation method thereof | |
| Yuanchun et al. | Preparation of cobalt oxide nanoparticles and cobalt powders by solvothermal process and their characterization | |
| Hu et al. | Nanostructural evolution: from one-dimensional tungsten oxide nanowires to three-dimensional ferberite flowers | |
| CN105834446B (en) | A kind of synthetic method of ultra-thin stratiform NiO CoOx nanometer sheets load NiCo nano compositions | |
| Xiong et al. | Hydrothermal synthesis and characterization of Bi2Fe4O9 nanoparticles | |
| CN104117683B (en) | Six side's phase cobalt-nickel alloy nano-cluster-graphene composite materials, Preparation Method And The Use | |
| CN104043840B (en) | Emission in Cubic cobalt-nickel alloy nano-cluster-graphene composite material, Preparation Method And The Use | |
| Lee et al. | Unique multi-phase Co/Fe/CoFe2O4 by water–gas shift reaction, CO oxidation and enhanced supercapacitor performances | |
| CN102659188A (en) | Magnetic ferric oxide micrometer flower material with multi-stage structure and preparation method thereof | |
| Yakout | Inclusion of cobalt reinforced Ag doped SnO 2 properties: electrical, dielectric constant, magnetic and photocatalytic insights | |
| CN105817648A (en) | Iron-nickel alloy nanocluster-graphene composite material and preparation method and application thereof | |
| Nam et al. | One-step structure modulation of electrospun metal-loaded carbon nanofibers: Redox reaction controlled calcination | |
| CN109604628A (en) | A kind of preparation method of ordered phase nanometer Fe-Pt particle and cobalt platinum nano particle | |
| Ning et al. | Facile synthesis of magnetic metal (Mn, Fe, Co, and Ni) oxides nanocrystals via a cation-exchange reaction | |
| Roy et al. | Effect of interstitial oxygen on the crystal structure and magnetic properties of Ni nanoparticles | |
| KR20130075115A (en) | Method for preparing znco2o4 nanoparticle by a reverse micelle process and znco2o4 nanoparticle prepared therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140416 Termination date: 20180802 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |