CN102796999B - 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
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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
Such as Graphenes of two-dimensional nano material etc. are because of its unique physics, chemical property and extremely people's concern of application prospect widely.The metallic sulfide of two dimension super-thin sheet-shaped has high energy/electron storage specific volume; The ultrathin section that the discoveries such as H.Welle are assembled into by nano unit, not only can keep the Quantum Properties of zero-dimension nano unit, and owing to making ultrathin section layer material have good mechanical property and electron transport ability concurrently in the stretching, extension of two-dimensional space.At present, preparation method is single for two dimension layer material, be mainly take smooth solid phase template as substrate, to pass through physics, electroless plating or crystal growth preparation, the two-dimentional ultrathin section layer material that wish obtains self-supporting need to pass through the loaded down with trivial details template procedure that goes, thereby has restricted the application of two-dimensional slices material.
Transition metal (iron, cobalt, the nickel) material of nano-scale has good chemistry and physicals, in fields such as catalysis, electronics, magnetics, has good application prospect.But; due to transition metal (iron, cobalt, nickel) self structure feature and oxidizable characteristic; the nano material of the transition metal (iron, cobalt, nickel) of having reported mostly at present is the nanoparticle of tensio-active agent protection; wherein nanometer sheet mostly is hard template preparation; obtain separately can self-supporting nano flake need slough template; method technique is loaded down with trivial details, and take interface as two-dimentional self-supporting transition metal (iron, cobalt, the nickel) ultrathin section of guiding preparation has not yet to see report.
Summary of the invention
To the object of the invention is to have in order solving in existing two-dimentional self-supporting transition metal ultrathin section preparation method the problem that technique is loaded down with trivial details, thereby a kind of preparation method of two-dimentional self-supporting transition metal ultrathin section to be provided.
In the present invention, a kind of 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, 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 the dirty solution of the organic amine title complex that contains metal ion, in dirty solution, add non-polar organic solvent, low whipping speed is to stir 0.5 ~ 10min under 300 ~ 800r/min condition, after standing 5 ~ 15min, the organic amine title complex non-polar organic solutions of the metal ion obtaining, organic phase is transferred in airtight reflux,
Two, under protection of inert gas, at 15 ~ 99 ℃, stirring velocity is stirring and refluxing 15min under 300 ~ 800r/min condition, take the rate of addition of 20 ~ 100mL/h, in the reaction system after refluxing, add concentration as 0.001 ~ 0.1mol/L sodium borohydride frozen water solution, making the mol ratio of the transition metal inorganic salt that add in the sodium borohydride that adds and step 1 is 5 ~ 15:1, after dripping, continue reaction 0.5 ~ 2h, reaction product is cooled to 25 ℃, reaction product is separated and obtains sample, sample washing is placed on to vacuum-drying 0.5 ~ 2h in 50 ℃ ~ 80 ℃ vacuum drying ovens and obtains black powder,
Three, by step 2 gained black powder under protection of inert gas condition in tube furnace calcination process, obtain two-dimentional self-supporting transition metal ultrathin section;
Wherein the transition metal inorganic salt in step 1 are inorganic molysite, inorganic cobalt salt or inorganic nickel; Described inorganic molysite is one or more mixture of iron nitrate, Iron nitrate, iron(ic) chloride, iron protochloride, ferric sulfate and ferrous sulfate; The mixture of one or more that described inorganic cobalt salt is rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride and Cobaltous diacetate; Described inorganic nickel is one or more the mixture in nickelous nitrate, single nickel salt, nickel acetate and nickelous chloride;
Organic amine in step 1 is one or more the mixture in amino dodecane, tetradecy lamine, cetylamine and stearylamine;
In step 1, alcohol is a kind of in methyl alcohol, ethanol and propyl alcohol or several mixture wherein;
Non-polar organic solvent in step 1 is one or more the mixture in toluene, normal butane, Skellysolve A, normal hexane, hexanaphthene, tetracol phenixin and sherwood oil;
Rare gas element in step 2 and three is the mixed gas of one or more gases in nitrogen, argon gas and helium;
Sodium borohydride frozen water solution in step 2 is that temperature is the sodium borohydride aqueous solution of 0 ℃;
Separation in step 2 is that one or more in magnetic resolution, centrifugation and suction filtration separation method are combined with;
In step 3, roasting condition is 1 ~ 10 ℃/min of temperature rise rate, 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 that the organic amine title complex that contains transition metal (iron, cobalt, nickel) ion is reduced into metal nanoparticle, and under the guide effect of interface, realize 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 by heating, stir, pass into the conditions such as rare gas element, accelerate interfacial mass transfer speed and speed of response, make a large amount of nanoparticles under interfacial tension effect, be squeezed into the laminated structure of self-supporting, do not need to use hard template, therefore subsequent disposal is without going template, and technique is relatively simple, and cost is low; Three, the present invention is being prepared aspect two-dimensional metallic thin slice, and synthetic method novelty, exists 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.
Accompanying drawing explanation
Fig. 1 is the 50000 times of scanning electron microscope (SEM) photographs of self-supporting cobalt ultrathin section before the calcination process that obtains of test one step 2;
Fig. 2 is the 15000 times of transmission electron microscope pictures of self-supporting cobalt ultrathin section before the calcination process that obtains of test one step 2;
Fig. 3 is the 300000 times of transmission electron microscope pictures of self-supporting cobalt ultrathin section before the calcination process that obtains of test one step 2, and the illustration in Fig. 3 is the 800000 times of transmission electron microscope pictures of self-supporting cobalt ultrathin section before the calcination process that obtains of test one step 2;
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 of measuring under 300K;
Fig. 6 is test one step 3 40000 times of scanning electron microscope (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 a) the X-ray diffraction spectrum of testing the self-supporting cobalt ultrathin section obtaining before calcination process in a step 2, Fig. 7 is b) the X-ray diffraction spectrum of the self-supporting cobalt ultrathin section after 500 ℃ of calcination process in test one step 3, and Fig. 7 is c) 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 under 300K, to measure the back-shaped curve of magnetic hysteresis;
Fig. 9 is the 25000 times of transmission electron microscope pictures of self-supporting iron ultrathin section that obtain before 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 test three step 2 calcination process.
Embodiment
Embodiment one: in the present invention, a kind of preparation method of two-dimentional self-supporting transition metal ultrathin section is realized by following step:
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, 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 the dirty solution of the organic amine title complex that contains metal ion, in dirty solution, add non-polar organic solvent, low whipping speed is to stir 0.5 ~ 10min under 300 ~ 800r/min condition, after standing 5 ~ 15min, the organic amine title complex non-polar organic solutions of the metal ion obtaining, organic phase is transferred in airtight reflux,
Two, under protection of inert gas, at 15 ~ 99 ℃, stirring velocity is stirring and refluxing 15min under 300 ~ 800r/min condition, take the rate of addition of 20 ~ 100mL/h, in the reaction system after refluxing, add concentration as 0.001 ~ 0.1mol/L sodium borohydride frozen water solution, making the mol ratio of the transition metal inorganic salt that add in the sodium borohydride that adds and step 1 is 5 ~ 15:1, after dripping, continue reaction 0.5 ~ 2h, reaction product is cooled to 25 ℃, reaction product is separated and obtains sample, sample washing is placed on to vacuum-drying 0.5 ~ 2h in 50 ℃ ~ 80 ℃ vacuum drying ovens and obtains black powder,
Three, by step 2 gained black powder under protection of inert gas condition at tubular type kiln roasting, obtain two-dimentional self-supporting transition metal ultrathin section;
Wherein the transition metal inorganic salt in step 1 are inorganic molysite, inorganic cobalt salt or inorganic nickel; Described inorganic molysite is one or more mixture of iron nitrate, Iron nitrate, iron(ic) chloride, iron protochloride, ferric sulfate and ferrous sulfate; The mixture of one or more that described inorganic cobalt salt is rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride and Cobaltous diacetate; Described inorganic nickel is one or more the mixture in nickelous nitrate, single nickel salt, nickel acetate and nickelous chloride;
Organic amine in step 1 is one or more the mixture in amino dodecane, tetradecy lamine, cetylamine and stearylamine;
In step 1, alcohol is a kind of in methyl alcohol, ethanol and propyl alcohol or several mixture wherein;
Non-polar organic solvent in step 1 is one or more the mixture in toluene, normal butane, Skellysolve A, normal hexane, hexanaphthene, tetracol phenixin and sherwood oil;
Rare gas element in step 2 and three is the mixed gas of one or more gases in nitrogen, argon gas and helium;
Sodium borohydride frozen water solution in step 2 is that temperature is the sodium borohydride aqueous solution of 0 ℃;
Separation in step 2 is that one or more in magnetic resolution, centrifugation and suction filtration separation method are combined with;
In step 3, roasting condition is 1 ~ 10 ℃/min of temperature rise rate, 200 ~ 600 ℃ of maturing temperatures, inert atmosphere flow 20 ~ 1500mL/min, roasting time 5min ~ 10h.
When in present embodiment step 1, inorganic molysite is mixture, between each component, mix in any proportion;
When in present embodiment step 1, inorganic cobalt salt is mixture, between each component, mix in any proportion;
When in present embodiment step 1, inorganic nickel is mixture, between each component, mix in any proportion;
When the organic amine in present embodiment step 1 is mixture, between each component, mix in any proportion;
When in present embodiment step 1, alcohol is mixture, between each component, mix in any proportion;
When the non-polar organic solvent in present embodiment step 1 is mixture, between each component, mix in any proportion;
When the rare gas element in present embodiment step 2 and three is mixture, between each component, mix in any proportion.
Advantage of the present invention: one, the present invention utilizes water miscible strong reductant that the organic amine title complex that contains transition metal (iron, cobalt, nickel) ion is reduced into metal nanoparticle, and under the guide effect of interface, realize 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 by heating, stir, pass into the conditions such as rare gas element, accelerate interfacial mass transfer speed and speed of response, make a large amount of nanoparticles under interfacial tension effect, be squeezed into the laminated structure of self-supporting, do not need to use hard template, therefore subsequent disposal is without going template, and technique is relatively simple, and cost is low; Three, the present invention is being prepared aspect two-dimensional metallic thin slice, and synthetic method novelty, exists 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: present embodiment is different from embodiment one: in step 1, transition metal inorganic salt are mixed with to the solution that volumetric molar concentration is 0.01 ~ 0.05mol/L.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: in step 1, the mol ratio of transition metal inorganic salt and organic amine is 1:3.5 ~ 6.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: in step 1, the mol ratio of transition metal inorganic salt and organic amine is 1:5.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: in 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: present embodiment is different from one of embodiment one to five: in 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: present embodiment is different from one of embodiment one to six: add concentration as 0.01 ~ 0.05mol/L sodium borohydride frozen water solution take the rate of addition of 40 ~ 80mL/h in the reaction system after refluxing in step 2.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: add concentration as 0.03mol/L sodium borohydride frozen water solution take the rate of addition of 60mL/h in the reaction system after refluxing in step 2.Other step and parameter are identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: the roasting condition in 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: present embodiment is different from one of embodiment one to nine: the roasting condition in 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 completes according to the following steps:
One, the preparation of cobalt ion organic amine title complex: Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is joined in distilled water and dissolved, be mixed with the cobalt nitrate solution that cobalt ion volumetric molar concentration is 0.001mol/L; In 25 ℃ of room temperatures, stirring velocity, be under 300r/min condition, to adding isopyknic volumetric molar concentration in the aqueous solution of the above-mentioned Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 50mL, it is the ethanolic soln of 0.005mol/L oleyl amine, stir, mix 3min, obtain the organic amine title complex that contains cobalt metal ion; In the organic amine title complex of cobalt ion, add 50mL toluene, stir 5min, standing 15min layering, and with separating funnel, organic phase toluene layer is separated to the oleyl amine title complex of the cobalt ion that obtains being dissolved in toluene, transfer in sealing reflux, obtain being dissolved in the oleyl amine title complex of the cobalt ion in toluene;
Two, reduction: under nitrogen atmosphere protection, the oleyl amine title complex of step 1 gained is heated to 45 ℃, low whipping speed is stirring, backflow 15min under 300r/min condition; Continuing heated and stirred refluxes, take the rate of addition of 50mL/h, 20mL concentration is dropwise added as the sodium borohydride frozen water solution of 0.02mol/L simultaneously, add after reaction 2h, be cooled to 25 ℃ of room temperatures magnetic resolution and obtain black powder shape product, water, ethanol alternately wash 5 times, vacuum drying 2h at 50 ℃, obtains two-dimentional self-supporting cobalt ultrathin section;
Three, high-temperature roasting: under the condition that is 600mL/min at nitrogen atmosphere flow, heat-up rate with 10 ℃/min rises to 500 ℃ by 25 ℃ of room temperatures, in heat treatment step two, the two-dimentional self-supporting cobalt ultrathin section 2h of preparation, obtains the two-dimentional self-supporting cobalt ultrathin section after thermal treatment;
In this testing sequence one, the mol ratio of organic amine and cobalt salt is 1:5;
In this testing sequence one, alcoholic solvent is 1:1 with adding the volume ratio of water;
In this testing sequence one, non-polar organic solvent is 1:1 with adding the volume ratio of water;
The mol ratio of the cobalt ion that the sodium borohydride adding in this testing sequence two and step 1 add is 1:8.
The two-dimentional self-supporting cobalt ultrathin section obtaining in this testing sequence two is carried out to pattern test:
Fig. 1 is that in test one, step 2 obtains the 50000 times of scanning electron microscope (SEM) photographs of two-dimentional self-supporting cobalt ultrathin section before calcination process, and as shown in Figure 1, the microscopic appearance of product is two-dimensional layered structure, and lamella is thinner, and lamella size is single, has good dispersity;
Fig. 2 is 15000 times of transmission electron microscope pictures of two-dimentional self-supporting cobalt ultrathin section before the calcination process that in test one, step 2 obtains, and as shown in Figure 2, sample is two-dimensional sheet structure, and lamella is approximately several microns, goes out to estimate thickness be about 2nm from fold;
Fig. 3 is 300000 times of transmission electron microscope pictures of two-dimentional self-supporting cobalt ultrathin section before the calcination process that in test one, step 2 obtains, and as shown in Figure 3, two-dimentional self-supporting cobalt ultrathin section is piled up and formed by nanometer small-particle, 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, and from Fig. 3 illustration, spacing of lattice d=0.216nm is Co(100) spacing of crystal face, spacing of lattice d=0.41nm is CoCo
2O3the spacing of crystal face, this is because the cobalt ultrathin section preparing is more active, is exposed to surface part in air and is oxidized to CoCo
2o
3;
Fig. 4 is that before the calcination process that in a pair of test of test, step 2 obtains, two-dimentional self-supporting cobalt ultrathin section carries out energy spectrum analysis figure, and as shown in Figure 4, sample is comprised 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, and this is because cobalt sheet is exposed in air, make surface form the oxide film of one deck densification, the inside of lamella still exists with the form of cobalt simple substance;
Fig. 5 is the test pattern that has carried out the back-shaped curve of magnetic hysteresis to testing two-dimentional self-supporting cobalt ultrathin section before the calcination process that in, step 2 obtains, as shown in Figure 5, the B-H loop of the back-shaped curve of magnetic hysteresis is closed hoop, explanation two-dimentional self-supporting cobalt ultrathin section under 300K has superparamagnetism, has good magnetic performance;
Fig. 6 carries out 40000 times of electron-microscope scanning figure to testing the two-dimentional self-supporting cobalt ultrathin section after step 3 thermal treatment in, and known to 6, after the thermal treatment of 500 ℃, sheet structure remains unchanged substantially, but has occurred spherical reunion;
The two-dimentional self-supporting cobalt ultrathin section of testing before and after a thermal treatment has been carried out to X-ray diffraction spectroscopic analysis:
Fig. 7 is a) the X-ray diffraction spectrum of step 2 without the two-dimentional self-supporting cobalt ultrathin section sample of Overheating Treatment, and as seen from the figure, sample, without X-ray diffraction peak, is that degree of crystallinity is not high because sample is to consist of crystallite particle, and lamella is thinner to be caused;
Fig. 7 is b) the X-ray diffraction spectrum of the two-dimentional self-supporting cobalt ultrathin section sample of step 3 after 500 ℃ of thermal treatments, the diffraction peak of cobalt simple substance as we can see from the figure, while, with the X-ray diffraction peak of the oxide compound of cobalt, shows that thermal treatment has improved the degree of crystallinity of cobalt ultrathin section;
Fig. 8 is the test pattern that has carried out the back-shaped curve of magnetic hysteresis to testing the two-dimentional self-supporting cobalt ultrathin section after step 3 thermal treatment in, as seen from the figure, the back-shaped curve of magnetic hysteresis has obvious B-H loop, explanation shows ferromegnetism through 500 ℃ of heat treated two-dimentional self-supporting cobalt ultrathin sections under 300K, shows 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 completes according to the following steps:
One, the preparation of iron ion organic amine title complex: iron(ic) chloride is joined in distilled water and dissolved, be mixed with the ferric chloride Solution that iron ion volumetric molar concentration is 0.001mol/L; 25 ℃ of room temperatures, under stirring velocity 300r/min condition, to adding isopyknic concentration in the aqueous solution of above-mentioned 50mL iron(ic) chloride, be the ethanolic soln of 0.0035mol/L oleyl amine, stir 3min, obtain the organic amine title complex that contains iron ion; In the organic amine title complex of iron ion, add 50mL toluene, stir 5min, standing 15min layering, and organic phase is separated and transferred in sealing reflux with separating funnel, obtain being dissolved in iron ion in toluene oleyl amine title complex;
Two, reduction: under nitrogen atmosphere protection, the oleyl amine title complex of step 1 gained is heated to 65 ℃, low whipping speed is stirring, backflow 15min under 300r/min condition, continue heating, stir, reflux, take the rate of addition of 50mL/h, 20mL concentration is dropwise added as the sodium borohydride frozen water solution of 0.02mol/L simultaneously, after reaction 2h, be cooled to 25 ℃ of room temperatures magnetic resolution and obtain black powder shape product, water, ethanol alternately wash 5 times, vacuum drying 2h at 50 ℃, obtains two-dimentional self-supporting iron ultrathin section;
Three, high-temperature roasting: be under 600mL/min condition at nitrogen atmosphere flow, heat-up rate with 10 ℃/min rises to 500 ℃ by 25 ℃ of room temperatures, in heat treatment step two, the two-dimentional self-supporting iron ultrathin section 2h of preparation, obtains the two-dimentional self-supporting iron ultrathin section after thermal treatment;
The mol ratio that adds organic amine and molysite in this testing sequence one 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 two, adding the mol ratio of the iron ion that sodium borohydride and step 1 add is 1:8.
The two-dimentional self-supporting iron ultrathin section that this testing sequence two is obtained carries out pattern test:
Fig. 9 is the 25000 times of scanning electron microscope (SEM) photographs of two-dimentional self-supporting iron ultrathin section that obtain before step 2 calcination process in test two, and as seen from the figure, the microscopic appearance of product is two-dimensional layered structure, and lamella is thinner, and lamella size is single, has good dispersity.
Test three: a kind of preparation method of two-dimentional self-supporting transiting metal nickel ultrathin section, specifically completes according to the following steps:
One, the preparation of nickel ion organic amine title complex: nickelous chloride is joined in distilled water and dissolved, be mixed with the nickel chloride solution that nickel ion volumetric molar concentration is 0.001mol/L; At 25 ℃ of room temperatures, under stirring velocity 300r/min condition, to adding isopyknic volumetric molar concentration in the aqueous solution of the nickelous chloride of above-mentioned 50mL, be the ethanolic soln of 0.0035mol/L oleyl amine, stir 3min, obtain the organic amine title complex that contains metal ion nickel; In the organic amine title complex of nickel ion, add toluene, stir 5min, standing 15min layering, and with separating funnel, organic phase is separated and transferred in sealing reflux, obtain being dissolved in the oleyl amine title complex of the nickel ion in toluene;
Two, reduction: under nitrogen atmosphere protection, the oleyl amine title complex of step 1 gained is heated to 45 ℃, stirring velocity is stirring, backflow 15min under 300r/min condition; Continue heating, stir, reflux, take the rate of addition of 50mL/h, 20mL concentration is dropwise added as the sodium borohydride frozen water solution of 0.02mol/L simultaneously, after reaction 2h, be cooled to 25 ℃ of room temperatures magnetic resolution and obtain black powder shape product, water, ethanol alternately wash 5 times, vacuum drying 2h at 50 ℃, obtains two-dimentional self-supporting nickel ultrathin section;
Three, high-temperature roasting: be under 600mL/min condition at nitrogen atmosphere flow, rise to 500 ℃ with the heat-up rate of 10 ℃/min by room temperature, in heat treatment step two, the two-dimentional self-supporting nickel ultrathin section 2h of preparation, obtains the two-dimentional self-supporting nickel ultrathin section after thermal treatment;
In this testing sequence one, 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 two, in sodium borohydride and step 1, the mol ratio of nickel ion is 1:8.
The two-dimentional self-supporting nickel ultrathin section that this testing sequence two is obtained carries out pattern test:
Figure 10 is the 15000 times of scanning electron microscope (SEM) photographs of two-dimentional self-supporting nickel ultrathin section that obtain before step 2 calcination process in test three, as seen from the figure, the microscopic appearance of product is two-dimensional layered structure with a little nanoparticle, and lamella is thinner, lamella size is single, has good dispersity.
Test four: a kind of preparation method of two-dimentional self-supporting transition metals cobalt ultrathin section, specifically completes according to the following steps:
One, the preparation of cobalt ion organic amine title complex: Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is joined in distilled water and dissolved, be configured to the cobalt nitrate solution that cobalt ion volumetric molar concentration is 0.001mol/L; Under 25 ℃ of room temperatures, stirring velocity 300r/min condition, to adding isopyknic volumetric molar concentration in the aqueous solution of the above-mentioned Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 50mL, be the ethanolic soln of 0.005mol/L oleyl amine, stir, mix 3min, obtain the organic amine title complex that contains cobalt ion; In the organic amine title complex of cobalt ion, add 50mL toluene, stir 5min, standing 15min layering, and with separating funnel, organic phase toluene layer is separated to the oleyl amine title complex of the cobalt ion that obtains being dissolved in toluene, after transfer in sealing reflux, obtain being dissolved in cobalt ion in toluene oleyl amine title complex;
Two, reduction: under nitrogen atmosphere protection, the oleyl amine title complex of step 2 gained is heated to 45 ℃, stirring velocity 300r/min stirs, backflow 15min; Continuing heated and stirred refluxes, take the rate of addition of 50mL/h, 20mL concentration is dropwise added as the sodium borohydride frozen water solution of 0.02mol/L simultaneously, react afterwards after 2h, be cooled to 25 ℃ of room temperatures magnetic resolution and obtain black powder shape product, water, ethanol alternately wash 5 times, vacuum drying 2h at 50 ℃, obtains two-dimentional self-supporting cobalt ultrathin section;
Three, high-temperature roasting: be under 600mL/min condition at nitrogen atmosphere flow, rise to 600 ℃ with the heat-up rate of 10 ℃/min by room temperature, in heat treatment step two, the two-dimentional self-supporting cobalt ultrathin section 2h of preparation, obtains the two-dimentional self-supporting cobalt ultrathin section after thermal treatment.
In this testing sequence one, the mol ratio of organic amine and cobalt salt is 1:5;
In this testing sequence one, alcoholic solvent is 1:1 with adding the volume ratio of water;
In this testing sequence one, non-polar organic solvent is 1:1 with adding the volume ratio of water;
The mol ratio of the cobalt ion that the sodium borohydride that this testing sequence two adds and step 1 add is 1:8.
Two-dimentional self-supporting cobalt ultrathin section before and after this test thermal treatment has been carried out to X-ray diffraction spectroscopic analysis, Fig. 7 is c) the X-ray diffraction spectrum of the two-dimentional self-supporting cobalt ultrathin section sample of step 3 after 700 ℃ of thermal treatments, as seen from the figure, see the diffraction peak of cobalt simple substance, while, with the X-ray diffraction peak of the oxide compound of cobalt, shows that thermal treatment has improved the degree of crystallinity of cobalt ultrathin section.
Claims (9)
1. a preparation method for 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 0.01～0.05mol/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, 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 the dirty solution of the organic amine title complex that contains metal ion, in dirty solution, add non-polar organic solvent, low whipping speed is to stir 0.5～10min under 300～800r/min condition, after standing 5～15min, the organic amine title complex non-polar organic solutions of the metal ion obtaining, organic phase is transferred in airtight reflux,
Two, under protection of inert gas, at 15～99 ℃, stirring velocity is stirring and refluxing 15min under 300～800r/min condition, take the rate of addition of 20～100mL/h, in the reaction system after refluxing, add concentration as 0.001～0.1mol/L sodium borohydride frozen water solution, making the mol ratio of the transition metal inorganic salt that add in the sodium borohydride that adds and step 1 is 5～15:1, after dripping, continue reaction 0.5～2h, reaction product is cooled to 25 ℃, reaction product is separated and obtains sample, sample washing is placed on to vacuum-drying 0.5～2h in 50 ℃～80 ℃ vacuum drying ovens and obtains black powder,
Three, by step 2 gained black powder under protection of inert gas condition at tubular type kiln roasting, obtain two-dimentional self-supporting transition metal ultrathin section;
Wherein the transition metal inorganic salt in step 1 are inorganic molysite, inorganic cobalt salt or inorganic nickel; Described inorganic molysite is one or more mixture of iron nitrate, Iron nitrate, iron(ic) chloride, iron protochloride, ferric sulfate and ferrous sulfate; The mixture of one or more that described inorganic cobalt salt is rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride and Cobaltous diacetate; Described inorganic nickel is one or more the mixture in nickelous nitrate, single nickel salt, nickel acetate and nickelous chloride;
Organic amine in step 1 is one or more the mixture in amino dodecane, tetradecy lamine, cetylamine and stearylamine;
In step 1, alcohol is a kind of in methyl alcohol, ethanol and propyl alcohol or several mixture wherein;
Non-polar organic solvent in step 1 is one or more the mixture in toluene, normal butane, Skellysolve A, normal hexane, hexanaphthene, tetracol phenixin and sherwood oil;
Rare gas element in step 2 and three is the mixed gas of one or more gases in nitrogen, argon gas and helium;
Sodium borohydride frozen water solution in step 2 is that temperature is the sodium borohydride aqueous solution of 0 ℃;
Separation in step 2 is that one or more in magnetic resolution, centrifugation and suction filtration separation method are combined with;
In step 3, roasting condition is 1～10 ℃/min of temperature rise rate, 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 step 1, the mol ratio of transition metal inorganic salt and organic amine is 1:3.5～6.
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 in step 1, the mol ratio of transition metal inorganic salt and organic amine is 1:5.
4. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 2, is characterized in that, in step 1, organic amine and alcohol are hybridly prepared into the organic amine alcoholic solution that concentration is 0.05～0.15mol/L.
5. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 4, is characterized in that, in step 1, organic amine and alcohol are hybridly prepared into the organic amine alcoholic solution that concentration is 0.10mol/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 step 2 in the reaction system after refluxing, adding concentration as 0.01～0.05mol/L sodium borohydride frozen water solution take the rate of addition of 40～80mL/h.
7. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 5, is characterized in that in step 2 in the reaction system after refluxing, adding concentration as 0.03mol/L sodium borohydride frozen water solution take the rate of addition of 60mL/h.
8. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 6, it is characterized in that the roasting condition in 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.
9. the preparation method of a kind of two-dimentional self-supporting transition metal ultrathin section according to claim 6, is characterized in that the roasting condition in step 3 is 5 ℃/min of temperature rise rate, 400 ℃ of maturing temperatures, inert atmosphere flow 800mL/min, roasting time 5h.
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