CN113441729A - Method for directly synthesizing high-coercivity non-noble metal nanowire by wet chemical method - Google Patents

Method for directly synthesizing high-coercivity non-noble metal nanowire by wet chemical method Download PDF

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CN113441729A
CN113441729A CN202110709281.8A CN202110709281A CN113441729A CN 113441729 A CN113441729 A CN 113441729A CN 202110709281 A CN202110709281 A CN 202110709281A CN 113441729 A CN113441729 A CN 113441729A
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裴文利
赵东
常玲
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Northeastern University China
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Abstract

The invention belongs to the technical field of magnetic nano materials, and particularly relates to a method for directly synthesizing a non-noble metal nanowire with high coercivity by a wet chemical method. The specific surfactant can enable the nano particles to directly grow according to the ordered structure under the appropriate reaction condition, and the nano particles directly have the ordered structure and high coercivity after growing into the nano wires without high-temperature ordered heat treatment. At the initial stage of the reaction, the metal precursor is reduced to form clusters, and then nanoparticles are grown. These nanoparticles are grown into nanowires by directional attachment under the condition of a surfactant. Adjusting the chemical components of the product by adjusting the proportion of the metal precursor; the appearance and coercive force of the product are controlled by adjusting the proportion of the solvent, the surfactant and the metal precursor, and the reaction temperature and time. The invention directly synthesizes the non-noble metal nanowire with high coercivity by a wet chemical method, the preparation is carried out at a lower synthesis temperature, the operation is simple, the coercivity effect of the synthesized non-noble metal nanowire is similar to that of an ordered structure intermetallic compound prepared by high-temperature annealing, but the shape is a one-dimensional shape which cannot be obtained by the high-temperature annealing method.

Description

Method for directly synthesizing high-coercivity non-noble metal nanowire by wet chemical method
The technical field is as follows:
the invention belongs to the technical field of magnetic nano materials, and particularly relates to a method for directly synthesizing a non-noble metal nanowire with high coercivity by a wet chemical method.
Background art:
the high-performance magnetic nanoparticles have special magnetic functional characteristics, so that the high-performance magnetic nanoparticles are key functional materials and research fronts in the field of magnetic application. The non-noble metal compounds of FeCo, FeNi, MnAl, MnGa, MnBi and the like with ordered structures have large magnetocrystalline anisotropy, high magnetic permeability and high Curie temperature. The material does not contain noble metal, has low cost, and particularly has the shape anisotropy when the shape is a nanowire, and the one-dimensional nanomaterial with the shape anisotropy has higher coercive force and squareness ratio, including the saturation magnetization related to the size and the magnetocrystalline anisotropy controlled by the shape. The one-dimensional nano material has obvious shape anisotropy, thereby leading to unique magnetic property and catalytic property. Therefore, the one-dimensional nano material prepared from the non-noble metal compound is expected to have wide application prospect in the fields of high-density magnetic storage, micro-nano magnetic devices, magneto-caloric therapy, image enhancement, DNA calibration and the like.
The performance and application of non-noble metal nano materials are closely connected with the structure, so that the non-noble metal nano wires with ordered structures need to be obtained for the practicability of the non-noble metal nano materials. Usually, non-noble metal nano materials with ordered structures are obtained, and high-temperature ordering heat treatment is needed to make atoms migrate and diffuse at high temperature to form interlayer alternate ordered structures of different atoms. But the high temperature causes the nano material to be spheroidized, grown and agglomerated. At present, non-noble metal nanowires synthesized by a wet chemical method, a template method, an electrodeposition method and a hydrothermal method are all chemically disordered fcc structures, and the obtained nanowires belong to soft magnetic materials and have low coercive force. In order to obtain a high coercivity, it needs to be heat treated, but as previously described, the nanowires are spheroidized after heat treatment and cannot retain the original one-dimensional morphology. Namely, the contradiction between the fact that one-dimensional morphology cannot be prepared at high temperature and the fact that ordered structures cannot be obtained at low temperature is formed, and the bottleneck problem which troubles researchers is how to directly synthesize the non-noble metal nanowire with high coercivity.
The invention content is as follows:
the invention aims to provide a method for directly synthesizing non-noble metal nanowires with high coercivity by a wet chemical method. The prepared nano-wire directly has an ordered structure, does not need high-temperature annealing, and can maintain a one-dimensional nano-structure.
The idea of the invention patent is as follows:
the shape anisotropy of the one-dimensional nanostructures can improve numerous physical properties of the nanomaterial. However, it is difficult to directly synthesize non-noble metal nanowires by chemical methods due to the synthetic difficulties associated with inducing anisotropic growth while controlling the multielement composition. Therefore, the linear alkylamine is used as a solvent, a specific surfactant is used as a capping agent in the synthesis process to have a preferential adsorption effect on different crystal faces, the crystal faces preferentially adsorbed can gather a large amount of surfactants, the crystal faces can be reduced, and the growth speed is slowed. The non-preferential adsorption crystal face only has a small amount of surfactant, the crystal face energy is high, the growth speed is high, and therefore the control of the morphology and the size of the nano crystal grains is achieved. At the initial stage of the reaction, the metal precursor is reduced to form clusters, and then nanoparticles are grown. These nanoparticles are grown into nanowires by directional attachment under the condition of a surfactant. Adjusting the chemical components of the product by adjusting the proportion of the metal precursor; the appearance and coercive force of the product are controlled by adjusting the proportion of the solvent, the surfactant and the metal precursor, and the reaction temperature and time.
In order to achieve the purpose, the invention adopts a method for directly synthesizing the non-noble metal nanowire with high coercivity by a wet chemical method to directly synthesize the non-noble metal nanowire with uniform appearance and high coercivity. Firstly, adding a metal precursor, a reducing agent and a solvent in a certain proportion into a solvent, mechanically stirring uniformly, removing water, then adding a certain amount of surfactant, heating the mixed solution at a slow heating rate to a certain temperature, preserving heat, and finally carrying out centrifugal cleaning on the obtained black solution through chloroform and absolute ethyl alcohol to obtain the non-noble metal nanowire. Specifically, the method comprises the following steps:
(1) weighing the metal precursor and the reducing agent according to the proportion, wherein the molar ratio of the metal ions in the metal precursor to the reducing agent is preferably 1: (0.2-2). The metal precursor is a metal source mixture of two non-noble metals capable of forming an ordered structure intermetallic compound, and the ordered structure intermetallic compound comprises FeCo, FeNi, MnAl, MnGa, MnBi and the like, so the metal precursor can be one of a mixture of an iron source and a cobalt source, a mixture of an iron source and a nickel source, a mixture of a manganese source and an aluminum source, a mixture of a manganese source and a gallium source or a mixture of a manganese source and a bismuth source, and in the metal precursor, namely the two metal sources, the molar ratio of two metal ions is preferably (0.1-1): (0.1-1), and the chemical components of the product can be adjusted by adjusting the molar ratio of the two metal ions.
(2) Adding a metal precursor and a reducing agent into a solvent to form a mixed solution, and then carrying out water removal treatment according to a molar ratio (metal ions in the metal precursor + the reducing agent): solvent 1: (10-40).
(3) In terms of mole ratio, surfactant: solvent 1: (1-10), adding a surfactant into the dehydrated mixed solution, uniformly mixing, and heating to 260-360 ℃, wherein the heating rate can be 1-10 ℃/min. And (3) heating, preserving the temperature for 30-300 min to obtain a black mixed solution, and cooling to room temperature.
(4) And carrying out centrifugal cleaning on the black mixed solution to obtain black powder, namely the high-coercivity non-noble metal nanowire.
In the step (1), the iron source can be ferric acetylacetonate Fe (acac)3FeCl, iron chloride3Iron sulfide Fe2(SO4)3Or iron nitrate Fe (NO)3)3The nickel source can be ferric acetylacetonate Ni (acac)2The manganese source can be ferric acetylacetonate Mn (acac)2The aluminum source can be acetylacetone iron Al (acac)3Gallium (III)The source may be iron acetylacetonate Ga (acac)3The bismuth source can be ferric acetylacetonate Bi (acac)3The cobalt source can be cobalt acetylacetonate Co (acac)2Cobalt chloride, CoCl2Cobalt sulfate CoSO4Or cobalt nitrate Co (NO)3)2One or more of (a).
In the step (1), the reducing agent is 1, 2-hexadecanediol C16H34O2Glucose C6H12O6Ascorbic acid C6H8O6Or sodium borohydride NaBH4One of (1) and (b).
In the step (2), the solvent is icosaediamine C22H47N, octadecylamine C18H39N, hexadecylamine C16H35N or trioctylamine C24H51One of N. Under a specific solvent and a specific growth environment of the nanowire, different crystal faces are assisted to adsorb different amounts of surfactants, so that the growth direction of the nanowire is regulated and controlled.
In the step (2), water removal can be performed in a heating mode, the heating temperature is 100-120 ℃, the heat preservation time is 30-60 min, the heating operation is performed under a protective atmosphere, and the flow rate of the protective atmosphere is 10-60 mu l/min. The protective atmosphere is preferably 95% Ar + 5% H2、93％Ar+7％H2High purity argon Ar or high purity nitrogen N2One of (1) and (b). The above gas percentages are by volume.
In the step (3), the surfactant is two of oleylamine OAm, oleic acid OA, cetyl trimethyl ammonium bromide CTAB and cetyl trimethyl ammonium chloride CTAC, and the two are preferably mixed according to the volume ratio of (1-5): (5-1) adding the dehydrated mixed solution. In the synthesis process of the nanowire, different crystal faces may adsorb different amounts of surfactants, so that the growth direction of the nanowire is regulated.
In the step (4), the method for obtaining the black powder by performing centrifugal cleaning on the black mixed solution comprises the following steps:
adding a mixed solvent of absolute ethyl alcohol and chloroform into the black mixed solution product, and performing centrifugal separation, wherein the volume ratio of absolute ethyl alcohol to chloroform in the mixed solvent is (1-5): (5-1), mixed solvent: the volume ratio of the black mixed solution is (3-5): and 1, pouring out the supernatant centrifugate after centrifugal separation, washing and centrifugally separating by using the absolute ethyl alcohol and chloroform mixed solvent, repeating for 3-5 times to obtain the non-noble metal nanowire black powder, wherein the centrifugal speed is 4000-10000 rpm, and the single centrifugation time is 3-10 min.
By the method, the high-coercivity non-noble metal nanowire can be directly prepared at 260-360 ℃, the coercivity Hc of the nanowire reaches 0.6-2.0 kOe, the saturation magnetization Ms reaches 61.2-124.8 emu/g, and the nanowire is comparable to the annealing effect and can be directly applied.
The invention has the beneficial effects that:
(1) the high-coercivity non-noble metal nanowire is directly synthesized by a wet chemical method, the preparation is carried out at a lower synthesis temperature, the operation is simple, the coercivity effect of the synthesized non-noble metal nanowire is similar to that of an ordered structure intermetallic compound prepared by high-temperature annealing, but the shape is a one-dimensional shape which cannot be obtained by the high-temperature annealing method.
(2) By optimizing the synthesis process, the non-noble metal nanowire with high coercivity and more uniform appearance can be obtained.
(3) The invention promotes the practicability of the one-step synthesis technology of the non-noble metal nanowire with high coercivity, simplifies the prior process, further saves the cost and has important theoretical and application values.
Description of the drawings:
FIG. 1 is an XRD spectrum of a non-noble metal nanowire prepared by the method of example 1 of the present invention;
FIG. 2 is a hysteresis loop of a non-noble metal nanowire prepared by the method of example 1;
FIG. 3 is a TEM image of non-noble metal nanowires prepared by the method of example 1 of the present invention;
FIG. 4 is an XRD spectrum of a non-noble metal nanowire prepared by the method of example 2 of the present invention;
FIG. 5 is a hysteresis loop of a non-noble metal nanowire prepared by the method of example 2 of the present invention;
FIG. 6 is a TEM image of non-noble metal nanowires prepared by the method of example 2 of the present invention;
FIG. 7 is an XRD spectrum of a non-noble metal nanowire prepared by the method of example 3 of the present invention;
FIG. 8 is a hysteresis loop of non-noble metal nanowires prepared by the method of example 3 of the present invention;
fig. 9 is a TEM image of non-noble metal nanowires prepared by the method of example 3 of the present invention.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
In the following examples:
the preparation equipment is commercially available and can be purchased in the market, and the preparation equipment and the instrument comprise: a three-neck flask, a condenser pipe, an electronic balance, a mechanical stirring heating sleeve, a centrifuge and the like;
the iron chloride, iron sulfide, iron nitrate, iron acetylacetonate, cobalt chloride, cobalt sulfide, cobalt nitrate, 1, 2-hexadecanediol, glucose, ascorbic acid, sodium borohydride, behenyl amine, octadecylamine, hexadecyl amine, trioctyl amine, oleyl amine, oleic acid, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, high-purity argon, high-purity nitrogen and 95% Ar + 5% H adopted in the embodiment of the invention2、93％Ar+7％H2The absolute ethyl alcohol and the chloroform are purchased from the market;
a method for directly synthesizing non-noble metal nanowires with high coercivity by a wet chemical method comprises the following steps:
(1) according to the molar ratio of metal ions to reducing agent of 1: (0.2-2), weighing a metal precursor and a reducing agent, wherein the metal precursor comprises one of a mixture of an iron source and a cobalt source, a mixture of an iron source and a nickel source, a mixture of a manganese source and an aluminum source, a mixture of a manganese source and a gallium source or a mixture of a manganese source and a bismuth source, and the molar ratio of the two is (0.1-1): (0.1 to 1);
(2) in terms of molar ratio, (metal ion + reducing agent in metal precursor): solvent 1: (10-40) adding a metal precursor and a reducing agent into a solvent to form a mixed solution, and then performing water removal treatment, wherein the solvent is one of icosandiamine, octadecylamine, hexadecylamine and trioctylamine;
(3) in terms of mole ratio, surfactant: solvent 1: (1-10), adding a surfactant into the dehydrated mixed solution, uniformly mixing, heating to 260-360 ℃ at a heating rate of 1-10 ℃/min, preserving heat for 30-300 min to obtain a black mixed solution, and cooling to room temperature;
(4) and (4) centrifugally cleaning the black mixed solution to obtain black powder, namely the high-coercivity non-noble metal nanowire.
In the step (1), the iron source is ferric acetylacetonate Fe (acac)3FeCl, iron chloride3Iron sulfide Fe2(SO4)3Or iron nitrate Fe (NO)3)3One of the nickel source is acetylacetone iron Ni (acac)2The manganese source is acetylacetone iron Mn (acac)2The aluminum source is acetylacetone iron Al (acac)3The gallium source is acetylacetone iron Ga (acac)3The bismuth source is ferric acetylacetonate Bi (acac)3The cobalt source is cobalt acetylacetonate Co (acac)2Cobalt chloride, CoCl2Cobalt sulfate CoSO4Or cobalt nitrate Co (NO)3)2One of (1) and (b).
In the step (1), the reducing agent is 1, 2-hexadecanediol C16H34O2Glucose C6H12O6Ascorbic acid C6H8O6Or sodium borohydride NaBH4One of (1) and (b).
In the step (2), the solvent is icosaediamine C22H47N, octadecylamine C18H39N, hexadecylamine C16H35N or trioctylamine C24H51One of N.
In the step (2), water is removed by a heating mode, the heating temperature is 100-120 ℃, the heat preservation time is 30-60 min, the heating operation is carried out under the protective atmosphere, and the flow of the protective atmosphere is 10-60 mu l/min.
In the step (2), the protective atmosphere is 95% Ar + 5% H2、93％Ar+7％、H2High purity argon Ar or high purity nitrogen N2One of (1) and (b).
In the step (3), the surfactant is two of oleylamine OAm, oleic acid OA, cetyl trimethyl ammonium bromide CTAB and cetyl trimethyl ammonium chloride CTAC. The volume ratio of the two is (1-5): (5-1) adding.
Adding a mixed solvent of absolute ethyl alcohol and chloroform into the black mixed solution product, and performing centrifugal separation, wherein the volume ratio of absolute ethyl alcohol to chloroform in the mixed solvent is (1-5): (5-1), mixed solvent: the volume ratio of the black mixed solution is (3-5): and 1, pouring out the supernatant centrifugate after centrifugal separation, cleaning and centrifugally separating by using the anhydrous ethanol and chloroform mixed solvent, repeating for 3-5 times to obtain the non-noble metal nanowire black powder, wherein the centrifugal speed is 4000-10000 rpm, and the single centrifugation time is 3-10 min.
The magnetic performance of the non-noble metal nano-wire is measured by using a Vibrating Sample Magnetometer (VSM), the appearance of the non-noble metal nano-wire is observed by using a field emission Transmission Electron Microscope (TEM), and the phase of the nano-particle is analyzed by X-ray diffraction (XRD) to confirm that the non-noble metal nano-material is obtained.
The non-noble metal nano wire with high coercivity can be directly prepared by the steps, is equivalent to the annealing effect, and can be directly applied.
Example 1:
(1) weighing a metal precursor iron source ferric acetylacetonate Fe (acac) by adopting an electronic balance3And a metal precursor cobalt source cobalt acetylacetonate Co (acac)2And the molar ratio of the two is 0.3: 0.2, the reducing agent 1, 2-hexadecanediol, the metal precursor (iron source + cobalt source) powder and the reducing agent 1, 2-hexadecanediol were subsequently weighed in a molar ratio of 1: 1.2.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent hexadecylamine, wherein the molar ratio of the (metal precursor + the reducing agent) to the solvent is 1: 15 under the protection of high-purity argon with the gas flow rate of 20 mul/min. Heating the mixed solution to 110 ℃ through a heating jacket, and preserving heat for 30min for dewatering treatment.
(3) And then adding surfactants oleic acid and oleylamine into the mixed solution respectively according to the mol ratio (oleic acid + oleylamine): solvent 1: 10, oleic acid: oleylamine ═ 1: 1, and then heated to 280 ℃ at a rate of a temperature rise rate of 3 ℃/min. After keeping the temperature for 180min, the heating jacket was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution 5: 1, absolute ethyl alcohol: chloroform-1: 3, then, carrying out centrifugal separation by a centrifugal machine, wherein the centrifugal speed is 9000rpm, the centrifugal time is 3min, pouring out the upper layer of centrifugal liquid, and repeating the steps: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 4 times to obtain FeCo nanowires. An X-ray diffractometer (XRD) is used for characterizing the phase of the sample to be an FeCo phase, wherein the phase contains FeCo phase characteristic peaks (110) and (200), and an XRD spectrum is shown in figure 1. Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force Hc1.1kOe, a saturation magnetization Ms of 73.5emu/g, and a hysteresis loop as shown in FIG. 2. The appearance of the sample is observed to be a one-dimensional nanowire state through a field emission Transmission Electron Microscope (TEM), and a TEM image is shown in an attached figure 3. The Nano Letters 2014,14,6493-6498 documents mention that the coercivity of the intermetallic compound prepared by annealing is 0.8kOe, which is similar to the result in the embodiment.
Example 2:
(1) weighing a metal precursor iron source ferric acetylacetonate Fe (acac) by adopting an electronic balance3And a metal precursor cobalt source cobalt acetylacetonate Co (acac)2The molar ratio of the two is 1: 1, then weighing the reducing agent glucose, the molar ratio of the metal precursor (iron source + cobalt source) and the reducing agent glucose being 1: 1.4.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent octadecylamine, wherein the molar ratio of the (metal precursor + reducing agent) to the solvent is 1: 20 under the protection of high-purity nitrogen with the gas flow rate of 30 mul/min. Heating the mixed solution to 105 ℃ through a heating jacket, and preserving heat for 45min for water removal treatment.
(3) And then adding surfactants oleylamine and oleic acid into the mixed solution respectively according to the mol ratio of (oleylamine + oleic acid): solvent 1: 5, oleylamine: oleic acid 2: 3, and then heated to 320 ℃ at a rate of 5 ℃/min. After keeping the temperature for 180min, the heating jacket was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by adopting absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is as follows (the absolute ethyl alcohol and the chloroform): mixed solution ═ 4: 1, absolute ethyl alcohol: chloroform-1: and 5, centrifuging by using a centrifuge, wherein the centrifuging speed is 10000rpm, the centrifuging time is 5min, pouring out the upper-layer centrifugate, and repeating the steps of: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain FeCo nanowires. An X-ray diffractometer (XRD) is used for characterizing the phase of the sample to be an FeCo phase, wherein the phase contains FeCo phase characteristic peaks (110) and (200), and an XRD spectrum is shown in figure 4. Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force Hc1.1kOe, a saturation magnetization Ms of 82.9emu/g, and a hysteresis loop as shown in FIG. 5. The appearance of the sample is observed to be a one-dimensional nanowire state through a field emission Transmission Electron Microscope (TEM), and a TEM image is shown in figure 6. The Nano Letters 2014,14,6493-6498 documents mention that the coercivity of the intermetallic compound prepared by annealing is 0.8kOe, which is similar to the result in the embodiment.
Example 3:
(1) weighing a metal precursor iron source ferric acetylacetonate Fe (acac) by adopting an electronic balance3And a metal precursor cobalt source cobalt acetylacetonate Co (acac)2And the molar ratio of the two is 0.2: 0.3, the reducing agent ascorbic acid was subsequently weighed, the molar ratio of metal precursor (iron source + cobalt source) and reducing agent ascorbic acid being 1: 1.5.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with solvent trioctylamine, wherein the mol ratio of the (metal precursor + the reducing agent) to the solventThe molar ratio is 1: 30, 95% Ar + 5% H at a gas flow rate of 40. mu.l/min2Under the protection. Heating the mixed solution to 115 ℃ through a heating jacket, and preserving heat for 60min for water removal treatment.
(3) And then adding surfactants oleic acid and oleylamine into the mixed solution respectively according to the mol ratio (oleic acid + oleylamine): solvent 1: 10, oleic acid: oleylamine ═ 3: 2, then heating to 300 ℃ at a rate of 5 ℃/min. After keeping the temperature for 180min, the heating jacket was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution ═ 3: 1, absolute ethyl alcohol: chloroform-5: 1, then carrying out centrifugal separation by a centrifugal machine, wherein the centrifugal speed is 6000rpm, the centrifugal time is 10min, pouring out the upper layer of centrifugal liquid, and repeating the steps: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 5 times to obtain FeCo nanowires. An X-ray diffractometer (XRD) is used for characterizing the phase of the sample to be an FeCo phase, wherein the phase contains FeCo phase characteristic peaks (110) and (200), and an XRD spectrum is shown in figure 7. Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force Hc1.0kOe, a saturation magnetization Ms of 81.8emu/g, and a hysteresis loop as shown in FIG. 8. The appearance of the sample is observed to be a one-dimensional nanowire state through a field emission Transmission Electron Microscope (TEM), and a TEM image is shown in an attached figure 9. The Nano Letters 2014,14,6493-6498 documents mention that the coercivity of the intermetallic compound prepared by annealing is 0.8kOe, which is similar to the result in the embodiment.
Example 4:
(1) weighing metal precursor iron source ferric chloride FeCl by adopting electronic balance3And a metal precursor cobalt source cobalt chloride (CoCl)2And the molar ratio of the two is 0.2: 2, subsequently weighing a reducing agent sodium borohydride, wherein the molar ratio of the metal precursor (iron source + cobalt source) to the reducing agent sodium borohydride is 1: 0.2.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent octadecylamine, wherein the molar ratio of the (metal precursor + the reducing agent) to the solvent is1: 40, 93% Ar + 7% H at a gas flow rate of 10. mu.l/min2Under the protection. Heating the mixed solution to 120 ℃ through a heating jacket, and preserving heat for 60min for dewatering treatment.
(3) Subsequently, surfactants CTAB and CTAC were added to the mixed solution, respectively, in a molar ratio, (CTAB + CTAC): solvent 1: 10, by volume ratio, CTAB: CTAC ═ 1: 5, then heating to 360 ℃ at a heating rate of 10 ℃/min. After incubation for 120min, the heating mantle was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution ═ 3: 1, absolute ethyl alcohol: chloroform-2: and 3, centrifuging by using a centrifuge, wherein the centrifuging speed is 4000rpm, the centrifuging time is 10min, pouring out the upper-layer centrifugate, and repeating the steps of: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain FeCo nanowires. The phase of the sample is characterized by an X-ray diffractometer (XRD) to contain FeCo phase characteristic peaks (110) and (200). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 0.7kOe, and the saturation magnetization Ms was 61.2 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 5:
(1) weighing metal precursor iron source ferric sulfate Fe by adopting electronic balance2(SO4)3And a metal precursor cobalt source cobalt sulfate CoSO4And the molar ratio of the two is 1.8: 2, subsequently weighing the reducing agent glucose, the metal precursor (iron source + cobalt source) and the reducing agent glucose in a molar ratio of 1: 2.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with solvent trioctylamine, wherein the molar ratio of (the metal precursor + the reducing agent) to the solvent is 1: 10 under the protection of high-purity argon with the gas flow rate of 20 mul/min. Heating the mixed solution to 100 ℃ through a heating jacket, and preserving heat for 45min for dewatering treatment.
(3) Then adding surfactants oleylamine and CTAB into the mixed solution respectively, and mixing the mixture according to the molar ratio of (oleylamine + CTAB): solvent 1: 1, oleylamine: CTAB ═ 5: 1, and then heated to 340 ℃ at a rate of temperature rise of 1 ℃/min. After incubation for 240min, the heating mantle was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution 5: 1, absolute ethyl alcohol: 3 parts of chloroform: and 2, centrifuging by a centrifuge at the speed of 6000rpm for 5min, pouring out the supernatant centrifugate, and repeating the following steps: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain FeCo nanowires. The phase of the sample is characterized by an X-ray diffractometer (XRD) to contain FeCo phase characteristic peaks (110) and (200). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 1.2kOe, and the saturation magnetization Ms was 78.5 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 6:
(1) weighing iron source ferric nitrate Fe (NO) of metal precursor by adopting an electronic balance3)3And a metal precursor cobalt source cobalt nitrate Co (NO)3)2The molar ratio of the two is 2: 0.2, the reducing agent ascorbic acid was subsequently weighed, the molar ratio of metal precursor (iron source + cobalt source) and reducing agent ascorbic acid being 1: 1.5.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with solvent trioctylamine, wherein the molar ratio of (the metal precursor + the reducing agent) to the solvent is 1: 12 under the protection of high-purity nitrogen with the gas flow rate of 25 mul/min. Heating the mixed solution to 110 ℃ through a heating jacket, and preserving heat for 30min for dewatering treatment.
(3) Then adding surfactants CTAB and oleic acid into the mixed solution respectively according to the mol ratio (CTAB + oleic acid): solvent 1: 10, by volume ratio, CTAB: oleic acid 3: 1, and then heated to 260 ℃ at a rate of 8 ℃/min. After keeping the temperature for 180min, the heating jacket was removed.
(4) Cooling the obtained black mixed solutionCooling to room temperature, and then performing dispersion cleaning by adopting absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution ═ 3: 1, absolute ethyl alcohol: chloroform-2: 3, then, carrying out centrifugal separation by a centrifugal machine, wherein the centrifugal speed is 9000rpm, the centrifugal time is 3min, pouring out the upper layer of centrifugal liquid, and repeating the steps: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain FeCo nanowires. The phase of the sample is characterized by an X-ray diffractometer (XRD) to contain FeCo phase characteristic peaks (110) and (200). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 0.8kOe, and the saturation magnetization Ms was 124.8 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 7:
(1) weighing a metal precursor iron source ferric acetylacetonate Fe (acac) by adopting an electronic balance3And a metal precursor cobalt source cobalt acetylacetonate Co (acac)2And the molar ratio of the two is 0.5: 1, then weighing the reducing agent 1, 2-hexadecanediol, the metal precursor (iron source + cobalt source) and the reducing agent 1, 2-hexadecanediol in a molar ratio of 1: 1.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent of icosapendiamine, wherein the molar ratio of the (metal precursor + reducing agent) to the solvent is 1: 15, 95% Ar + 5% H at a gas flow rate of 30. mu.l/min2Under the protection. Heating the mixed solution to 105 ℃ through a heating jacket, and preserving heat for 45min for water removal treatment.
(3) And then adding surfactants oleic acid and oleylamine into the mixed solution respectively according to the mol ratio (oleic acid + oleylamine): solvent 1: 5, oleic acid: oleylamine ═ 1: 5, and then heated to 260 ℃ at a rate of 5 ℃/min. After 30min of incubation, the heating mantle was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution 5: 1, absolute ethyl alcohol: chloroform-1: 5, then throughCentrifuging by a centrifuge at 8000rpm for 5min, pouring out the supernatant, and repeating: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain FeCo nanowires. The phase of the sample is characterized by an X-ray diffractometer (XRD) to contain FeCo phase characteristic peaks (110) and (200). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 1.0kOe, and the saturation magnetization Ms was 120.6 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 8:
(1) weighing a metal precursor iron source ferric acetylacetonate Fe (acac) by adopting an electronic balance3And a metal precursor cobalt source cobalt acetylacetonate Co (acac)2And the molar ratio of the two is 0.2: 2, subsequently weighing a reducing agent sodium borohydride, wherein the molar ratio of the metal precursor (iron source + cobalt source) to the reducing agent sodium borohydride is 1: 0.5.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent hexadecylamine, wherein the molar ratio of the (metal precursor + the reducing agent) to the solvent is 1: 10 under the protection of high-purity argon with the gas flow rate of 20 mul/min. Heating the mixed solution to 110 ℃ through a heating jacket, and preserving heat for 30min for dewatering treatment.
(3) Then adding surfactants oleylamine and CTAB into the mixed solution respectively, and mixing the mixture according to the molar ratio of (oleylamine + CTAB): solvent 1: 10, oleic acid: oleylamine ═ 2: 1, and then heating to 300 ℃ at a rate of a temperature rise rate of 3 ℃/min. After incubation for 300min, the heating mantle was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution ═ 4: 1, absolute ethyl alcohol: chloroform-5: 1, then carrying out centrifugal separation by a centrifugal machine, wherein the centrifugal speed is 8000rpm, the centrifugal time is 10min, pouring out the upper layer of centrifugal liquid, and repeating the steps: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain FeCo nanowires. Characterization of sample phase containing FeCo by X-ray diffractometer (XRD)Phase characteristic peaks (110) and (200). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 2.0kOe, and the saturation magnetization Ms was 86.5 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 9:
(1) weighing a metal precursor iron source ferric acetylacetonate Fe (acac) by adopting an electronic balance3And a metal precursor nickel source nickel acetylacetonate Ni (acac)2And the molar ratio of the two is 0.2: 0.3, the reducing agent 1, 2-hexadecanediol, the metal precursor (iron source + nickel source) and the reducing agent 1, 2-hexadecanediol were subsequently weighed in a molar ratio of 1: 1.5.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent hexadecylamine, wherein the molar ratio of the (metal precursor + the reducing agent) to the solvent is 1: 20 under the protection of high-purity argon with the gas flow rate of 30 mul/min. Heating the mixed solution to 115 ℃ through a heating jacket, and preserving heat for 45min for dewatering treatment.
(3) Then, surfactants oleic acid and CTAB were added to the mixed solution, respectively, in a molar ratio, (oleic acid + CTAB): solvent 1: 8, oleic acid: oleylamine ═ 1: 2, and then heated to 300 ℃ at a rate of 6 ℃/min. After keeping the temperature for 180min, the heating jacket was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution ═ 3: 1, absolute ethyl alcohol: chloroform-1: and 2, centrifuging by a centrifuge at 8000rpm for 5min, pouring out the supernatant centrifugate, and repeating the following steps: and adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain the FeNi nanowire. And (3) characterizing the phase of the sample to be a FeNi phase by utilizing an X-ray diffractometer (XRD). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 1.0kOe, and the saturation magnetization Ms was 80.6 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 10:
(1) weighing a metal precursor manganese source acetylacetone manganese Mn (acac) by an electronic balance2And a metal precursor aluminum source aluminum acetylacetonate Al (acac)3And the molar ratio of the two is 0.3: 0.2, the reducing agent ascorbic acid, the metal precursor (source of manganese + source of aluminium) and the reducing agent ascorbic acid were subsequently weighed in a molar ratio of 1: 1.2.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with solvent trioctylamine, wherein the molar ratio of (the metal precursor + the reducing agent) to the solvent is 1: 15 under the protection of high-purity argon with the gas flow rate of 25 mul/min. Heating the mixed solution to 120 ℃ through a heating jacket, and preserving heat for 30min for dewatering treatment.
(3) Then adding surfactants oleylamine and CTAC into the mixed solution respectively, and mixing the mixture according to the molar ratio of (oleylamine + CTAC): solvent 1: 7, oleic acid: oleylamine ═ 1: 3, and then heating to 280 ℃ at a rate of 5 ℃/min. After incubation for 120min, the heating mantle was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution ═ 3: 1, absolute ethyl alcohol: chloroform-1: and 3, centrifuging by using a centrifuge at the speed of 6000rpm for 10min, pouring out the supernatant centrifugate, and repeating the following steps: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain the MnAl nanowire. And (3) characterizing the phase of the sample to be a MnAl phase by using an X-ray diffractometer (XRD). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 0.8kOe and the saturation magnetization Ms was 73.5 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 11:
(1) weighing a metal precursor manganese source acetylacetone iron manganese Mn (acac) by an electronic balance2And a metal precursor gallium source gallium acetylacetonate Ga (acac)3And the molar ratio of the two is 0.2: 0.3, followed by weighing the reductant boronThe molar ratio of sodium hydride, metal precursor (manganese source + gallium source) and reducing agent sodium borohydride is 1: 1.3.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent octadecylamine, wherein the molar ratio of the (metal precursor + reducing agent) to the solvent is 1: 16 under the protection of high-purity argon with the gas flow rate of 35 mul/min. Heating the mixed solution to 110 ℃ through a heating jacket, and preserving heat for 60min for water removal treatment.
(3) Subsequently, surfactants CTAB and CTAC were added to the mixed solution, respectively, in a molar ratio, (CTAB + CTAC): solvent 1: 5, oleic acid: oleylamine ═ 1: 4, and then heated to 320 ℃ at a rate of 3 ℃/min. After incubation for 200min, the heating mantle was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution ═ 3: 1, absolute ethyl alcohol: chloroform-1: and 2, centrifuging by using a centrifuge at the speed of 7000rpm for 8min, pouring out the supernatant centrifugate, and repeating the following steps: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain the MnGa nanowire. The phase of the sample was characterized as MnGa phase using X-ray diffractometer (XRD). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 0.9kOe, and the saturation magnetization Ms was 68.4 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 12:
(1) weighing a metal precursor manganese source acetylacetone iron manganese Mn (acac) by an electronic balance2And a metal precursor bismuth source bismuth acetylacetonate Bi (acac)3And the molar ratio of the two is 0.5: 0.6, then weighing the reducing agent glucose, the molar ratio of the metal precursor (source of manganese + source of bismuth) and the reducing agent glucose being 1: 2.0.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent of icosapendiamine, wherein the molar ratio of the (metal precursor + reducing agent) to the solvent is 1: 20 under the protection of high-purity argon with the gas flow rate of 30 mul/min. Heating the mixed solution to 110 ℃ through a heating jacket, and preserving heat for 30min for dewatering treatment.
(3) Then adding surfactants oleylamine and CTAB into the mixed solution respectively, and mixing the mixture according to the molar ratio of (oleylamine + CTAB): solvent 1: 6, oleic acid: oleylamine ═ 2: 3, and then heating to 280 ℃ at a rate of 5 ℃/min. After incubation for 120min, the heating mantle was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution ═ 4: 1, absolute ethyl alcohol: chloroform-1: and 3, centrifuging by using a centrifuge at the speed of 6000rpm for 8min, pouring out the supernatant centrifugate, and repeating the following steps: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 4 times to obtain the MnBi nanowire. And (3) characterizing the phase of the sample to be a MnBi phase by using an X-ray diffractometer (XRD). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 0.8kOe and the saturation magnetization Ms was 94.8 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 13:
(1) weighing a metal precursor iron source ferric acetylacetonate Fe (acac) by adopting an electronic balance3And a metal precursor nickel source nickel acetylacetonate Ni (acac)2And the molar ratio of the two is 0.3: 0.2, the reducing agent ascorbic acid, the metal precursor (iron source + nickel source) and the reducing agent ascorbic acid were subsequently weighed in a molar ratio of 1: 1.2.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent octadecylamine, wherein the molar ratio of the (metal precursor + reducing agent) to the solvent is 1: 30 under the protection of high-purity argon with the gas flow rate of 20 mul/min. Heating the mixed solution to 115 ℃ through a heating jacket, and preserving heat for 30min for dewatering treatment.
(3) Then adding surfactants oleylamine and CTAC into the mixed solution respectively, and mixing the mixture according to the molar ratio of (oleylamine + CTAC): solvent 1: 3, oleic acid: oleylamine ═ 3: 2, and then heated to 300 ℃ at a rate of 6 ℃/min. After 160min of incubation, the heating mantle was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution ═ 4: 1, absolute ethyl alcohol: chloroform-1: 3, then, carrying out centrifugal separation by a centrifugal machine, wherein the centrifugal speed is 9000rpm, the centrifugal time is 3min, pouring out the upper layer of centrifugal liquid, and repeating the steps: and adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain the FeNi nanowire. And (3) characterizing the phase of the sample to be a FeNi phase by utilizing an X-ray diffractometer (XRD). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 1.6kOe, and the saturation magnetization Ms was 70.6 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 14:
(1) weighing a metal precursor manganese source acetylacetone manganese Mn (acac) by an electronic balance2And a metal precursor aluminum source aluminum acetylacetonate Al (acac)3And the molar ratio of the two is 0.2: 0.3, then the reducing agent 1, 2-hexadecanediol, the metal precursor (manganese source + aluminum source) and the reducing agent 1, 2-hexadecanediol were weighed in a molar ratio of 1: 1.5.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent of icosapendiamine, wherein the molar ratio of the (metal precursor + reducing agent) to the solvent is 1: 13 under the protection of high-purity argon with the gas flow rate of 20 mul/min. Heating the mixed solution to 110 ℃ through a heating jacket, and preserving heat for 60min for water removal treatment.
(3) Then, surfactants oleic acid and CTAB were added to the mixed solution, respectively, in a molar ratio, (oleic acid + CTAB): solvent 1: 2, oleic acid: oleylamine ═ 1: 1, and then heated to 290 ℃ at a rate of 5 ℃/min. After incubation for 150min, the heating mantle was removed.
(4) Cooling the obtained black mixed solution to room temperature, then adopting absolute ethyl alcohol and chloroform to carry out dispersed cleaning,the addition amount of the absolute ethyl alcohol and the chloroform is (the absolute ethyl alcohol and the chloroform): mixed solution ═ 3: 1, absolute ethyl alcohol: chloroform-1: and 3, centrifuging by using a centrifuge, wherein the centrifuging speed is 9000rpm, the centrifuging time is 4min, pouring out the upper layer of the centrifugate, and repeating the steps of: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 3 times to obtain the MnAl nanowire. And (3) characterizing the phase of the sample to be a MnAl phase by using an X-ray diffractometer (XRD). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 1.8kOe and the saturation magnetization Ms was 75.5 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 15:
(1) weighing a metal precursor manganese source acetylacetone iron manganese Mn (acac) by an electronic balance2And a metal precursor gallium source gallium acetylacetonate Ga (acac)3And the molar ratio of the two is 0.2: 0.3, the reducing agent ascorbic acid, the metal precursor (source of manganese + source of gallium) and the reducing agent ascorbic acid were subsequently weighed in a molar ratio of 1: 1.5.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with a solvent octadecylamine, wherein the molar ratio of the (metal precursor + reducing agent) to the solvent is 1: 16 under the protection of high-purity argon with the gas flow rate of 30 mul/min. Heating the mixed solution to 110 ℃ through a heating jacket, and preserving heat for 60min for water removal treatment.
(3) Then adding surfactants oleylamine and CTAB into the mixed solution respectively, and mixing the mixture according to the molar ratio of (oleylamine + CTAB): solvent 1: 6, oleic acid: oleylamine ═ 2: 3, and then heated to 320 ℃ at a rate of 4 ℃/min. After keeping the temperature for 180min, the heating jacket was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution ═ 3: 1, absolute ethyl alcohol: chloroform-1: and 2, centrifuging by a centrifuge at 8000rpm for 5min, pouring out the supernatant centrifugate, and repeating the following steps: adding intoAnd dispersing and cleaning the mixture of absolute ethyl alcohol and chloroform, and performing centrifugal separation for 3 times to obtain the MnGa nanowire. The phase of the sample was characterized as MnGa phase using X-ray diffractometer (XRD). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIt was 1.9kOe, and the saturation magnetization Ms was 64.4 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
Example 16:
(1) weighing a metal precursor manganese source acetylacetone iron manganese Mn (acac) by an electronic balance2And a metal precursor bismuth source bismuth acetylacetonate Bi (acac)3And the molar ratio of the two is 0.6: 0.5, then weighing a reducing agent sodium borohydride, the molar ratio of the metal precursor (manganese source + bismuth source) and the reducing agent sodium borohydride being 1: 1.8.
(2) adding a metal precursor and a reducing agent into a three-neck flask filled with solvent trioctylamine, wherein the molar ratio of (the metal precursor + the reducing agent) to the solvent is 1: 15 under the protection of high-purity argon with the gas flow rate of 25 mul/min. Heating the mixed solution to 110 ℃ through a heating jacket, and preserving heat for 45min for water removal treatment.
(3) Then, surfactants oleic acid and CTAB were added to the mixed solution, respectively, in a molar ratio, (oleic acid + CTAB): solvent 1: 8, oleic acid: oleylamine ═ 3: 2, and then heated to 300 ℃ at a rate of 7 ℃/min. After incubation for 150min, the heating mantle was removed.
(4) Cooling the obtained black mixed solution to room temperature, and then performing dispersed cleaning by using absolute ethyl alcohol and chloroform, wherein the addition amount of the absolute ethyl alcohol and the chloroform is (absolute ethyl alcohol + chloroform): mixed solution 5: 1, absolute ethyl alcohol: chloroform-1: 2, then carrying out centrifugal separation by a centrifugal machine, wherein the centrifugal speed is 10000rpm, the centrifugal time is 3min, pouring out the upper layer of centrifugal liquid, and repeating: adding absolute ethyl alcohol and chloroform for dispersing and cleaning, and performing centrifugal separation for 4 times to obtain the MnBi nanowire. And (3) characterizing the phase of the sample to be a MnBi phase by using an X-ray diffractometer (XRD). Measuring the magnetic hysteresis loop of the sample at room temperature by using a Vibrating Sample Magnetometer (VSM), and the coercive force HcIs 1.6kOe and has a saturation magnetization Ms of69.5 emu/g. And observing the appearance of the sample into a one-dimensional nanowire state by a field emission Transmission Electron Microscope (TEM).
It can be seen from the above examples that the non-noble metal nanowires with high coercivity can be directly synthesized by a wet chemical method, and the performance is comparable to the annealing effect.

Claims (10)

1. A method for directly synthesizing a non-noble metal nanowire with high coercivity by a wet chemical method is characterized by comprising the following steps of:
(1) weighing a metal precursor and a reducing agent, wherein the metal precursor is a metal source mixture of two non-noble metals capable of forming an intermetallic compound with an ordered structure;
(2) adding a metal precursor and a reducing agent into a solvent to form a mixed solution, and then carrying out water removal treatment;
the solvent is icosadiamine C22H47N, octadecylamine C18H39N, hexadecylamine C16H35N or trioctylamine C24H51One of N;
(3) adding a surfactant into the dehydrated mixed solution, uniformly mixing, heating, keeping constant temperature at regular time to obtain a black mixed solution, and cooling to room temperature;
the surfactant is two of oleylamine OAm, oleic acid OA, cetyl trimethyl ammonium bromide CTAB and cetyl trimethyl ammonium chloride CTAC;
(4) and carrying out centrifugal cleaning on the black mixed solution to obtain black powder, namely the high-coercivity non-noble metal nanowire.
2. The method for directly synthesizing the non-noble metal nanowire with high coercivity by the wet chemical method as claimed in claim 1, wherein the metal precursor is one of a mixture of an iron source and a cobalt source, a mixture of an iron source and a nickel source, a mixture of a manganese source and an aluminum source, a mixture of a manganese source and a gallium source or a mixture of a manganese source and a bismuth source, and the molar ratio of two metal ions in the metal precursor is (0.1-1): (0.1 to 1).
3. The method for directly synthesizing high coercivity non-noble metal nanowires by wet chemical method according to claim 2, wherein the iron source is ferric acetylacetonate fe (acac)3FeCl, iron chloride3Iron sulfide Fe2(SO4)3Or iron nitrate Fe (NO)3)3The nickel source is nickel acetylacetonate Ni (acac)2The manganese source is acetylacetone manganese Mn (acac)2The aluminum source is aluminum acetylacetonate Al (acac)3The gallium source is acetylacetone gallium Ga (acac)3The bismuth source is bismuth acetylacetonate Bi (acac)3The cobalt source is cobalt acetylacetonate Co (acac)2Cobalt chloride, CoCl2Cobalt sulfate CoSO4Or cobalt nitrate Co (NO)3)2One or more of (a).
4. The method for the direct synthesis of high coercivity non-noble metal nanowires by wet chemistry according to claim 1, wherein the reducing agent is 1, 2-hexadecanediol C16H34O2Glucose C6H12O6Ascorbic acid C6H8O6Or sodium borohydride NaBH4The molar ratio of the metal ion and the reducing agent in the metal precursor is 1: (0.2-2).
5. The method for direct synthesis of high coercivity non-noble metal nanowires by wet chemistry according to claim 1, wherein in step (2), the ratio of metal ions in the metal precursor + reducing agent is (molar ratio): solvent 1: (10-40); in the step (3), two substances in the surfactant are mixed according to the volume ratio of (1-5): (5-1) adding; in molar ratio, surfactant: solvent 1: (1-10).
6. The method for directly synthesizing the non-noble metal nanowire with high coercivity by the wet chemical method according to claim 1, wherein the water removal treatment in the step (2) is performed by a heating mode, the heating temperature is 100-120 ℃, the heat preservation time is 30-60 min, the heating operation is performed under a protective atmosphere, and the flow rate of the protective atmosphere is 10-60 μ l/min.
7. The method for direct synthesis of high coercivity non-noble metal nanowires by wet chemistry according to claim 6, wherein the protective atmosphere is 95% Ar + 5% H2、93％Ar+7％H2High purity argon Ar or high purity nitrogen N2One of (1), the percentage is volume percentage.
8. The method for directly synthesizing the non-noble metal nanowire with high coercivity by the wet chemical method as claimed in claim 1, wherein in the step (3), the nanowire is heated to 260-360 ℃ at a heating rate of 1-10 ℃/min, and is kept at the temperature for 30-300 min.
9. The method for directly synthesizing the non-noble metal nanowire with high coercivity by the wet chemical method as claimed in claim 1, wherein the step (4) of centrifugally cleaning the black mixed solution to obtain the black powder comprises the following steps:
adding a mixed solvent of absolute ethyl alcohol and chloroform into the black mixed solution, and performing centrifugal separation, wherein the volume ratio of absolute ethyl alcohol to chloroform in the mixed solvent is (1-5): (5-1), mixed solvent: the volume ratio of the black mixed solution is (3-5): and 1, pouring out the supernatant centrifugate after centrifugal separation, washing and centrifugally separating by using the absolute ethyl alcohol and chloroform mixed solvent, repeating for 3-5 times to obtain the non-noble metal nanowire black powder, wherein the centrifugal speed is 4000-10000 rpm, and the single centrifugation time is 3-10 min.
10. A high coercivity non-noble metal nanowire prepared by the wet chemical process of any one of claims 1 to 9 for direct synthesis of high coercivity non-noble metal nanowires.
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