CN111943218B - Preparation method of nano transition metal boride - Google Patents
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Abstract
The invention discloses a preparation method of a nanometer transition metal boride. The preparation method comprises the following steps: introducing boron-containing gas into the nano transition metal oxide or transition metal simple substance for boronizing, then introducing inert gas, and cooling to obtain the nano transition metal boride; wherein the transition metal simple substance is prepared by reducing the nanometer transition metal oxide: and placing the nanometer transition metal oxide into a reactor, and introducing reducing gas for reduction to obtain the transition metal simple substance. The preparation temperature is low, and the size of the obtained transition metal boride can be controlled at a nanometer level; the product has high purity, and the phenomenon that a large amount of oxide is obtained by the traditional method is avoided; the method has strong applicability, and can be used for preparing various transition metal borides; simple steps, good repeatability and mass preparation.
Description
Technical Field
The invention relates to a preparation method of a nano transition metal boride, belonging to the technical field of catalytic material synthesis.
Background
Transition metal borides, due to their relatively high hardness, melting point, wear resistance, and excellent magnetic and electrical properties, are commonly used as superhard materials, superconducting materials, magnetic materials, and metal protective coatings in precision instruments, machining, metallurgy, and electrical engineering, The catalyst has important application in the fields of aerospace, catalysis and the like. Among them, the application of nano transition metal boride in catalysis and photoelectric materials is especially important. For example: the metal boride is a common hydrogenation and dehydrogenation catalyst, and shows excellent performance in the aspects of hydrogen storage, water electrolysis and the like; lanthanum hexaboride (LaB)6) There is no alternative position as light source material in electron microscope and energy spectrometer.
At present, the methods for industrially producing transition metal borides mainly comprise: high temperature solid phase methods, liquid phase synthesis methods, physical deposition methods, and chemical vapor deposition methods (CVD).
The high-temperature solid-phase process is usually carried out by reacting a metal salt or metal oxide with a solid reducing agent (C, B)4C, Mg, etc.) and elemental boron or boron oxide at high temperature (typically above 1000℃) to obtain the corresponding metal boride. Chinese patent CN102417188B discloses a method for preparing metal boride by a high-temperature solid phase method, which comprises the step of reacting transition metal oxide with simple substance boron at high temperature to prepare 200-700 nm transition metal boride in batches. Although the method has simple process, the product size is large, and the elemental boron in the reaction raw material is easy to oxidize to obtain boron oxide, thereby polluting the product. Chinese patent CN104961137B discloses a method for preparing nano alkaline earth metal boride, which is prepared by mixing alkaline earth metal oxide and NaBH 4Reacting at high temperature to obtain 10-150 nm of alkaline earth metal boride. In the method, reaction raw materials are all solid phases, and the pollution of Na in the product is difficult to avoid. In addition, the method has narrow application range and cannot be used for preparing transition metal boride. In conclusion, although the high-temperature solid phase method has simple operation conditions, the obtained product has large particle size, generally contains solid pollutants, and boride with a single phase is difficult to obtain, so that the application of the high-temperature solid phase method in the fields of precision devices, catalysis and the like is limited.
The liquid phase synthesis method generally uses a boron-containing reducing agent to reduce metal salt in an organic solvent, so that nanoparticles with smaller size can be obtained. Chinese patent CN1314483C discloses a method for synthesizing nano transition metal boride by low-temperature liquid phase, which comprises the steps of reacting borohydride with metal salt at room temperature, and then carrying out heat treatment at 50-900 ℃ to obtain the nano metal boride with excellent dehydrogenation and hydrogenation reaction catalytic performance. Chinese patent CN100402424C discloses a high-temperature liquid-phase synthesis method, namely, metal chloride reacts with sodium borohydride or potassium borohydride at the temperature of 500-600 ℃ to prepare nano hexaboride. The method has the defects of complex operation process or harsh conditions and the like in different degrees, and can not realize large-scale industrial production.
Physical deposition is generally carried out by spraying boron onto the metal surface at elevated temperature or under electrical discharge conditions to obtain a metal boride thin film material. Chinese patents CN104404467B and CN106119762B disclose a method for preparing transition metal boride films by high temperature spraying or magnetron sputtering, respectively, which are only suitable for the production of physical film materials. Chinese patent CN106011854B discloses a method for preparing a coating of an iron-boron compound, which utilizes an electric spark deposition process to obtain FeB and Fe2B and Fe3B, and is a dense coating.
The chemical vapor deposition method is to gasify metal salt and boron source at high temperature and then deposit in a deposition chamber, and although the method can regulate and control the particle size of the product, the method has strict requirements on raw materials and higher equipment cost, and is not suitable for large-scale industrial application. For example, chinese patent CN101855385 discloses a Chemical Vapor Deposition (CVD) method for the preparation of photovoltaic thin film materials, which can be used for boron doping in photovoltaic materials.
In the traditional preparation method, the high-temperature solid phase method can reach the scale of industrial application, but can not obtain the nano metal boride with higher purity; both the liquid phase synthesis method and the chemical vapor deposition method can only meet the requirement of laboratory scale production; physical and chemical deposition methods usually only dope the metal surface and cannot meet the requirements of material molding. Therefore, the invention is of great significance in the industrial batch production of the nano transition metal boride.
Disclosure of Invention
The invention aims to provide a preparation method of nano transition metal boride, which has the advantages of low preparation temperature, high product purity, simple operation, controllable grain size, wide substrate application range and the like, overcomes the defects of complex process, harsh preparation conditions, impure product and the like of the traditional preparation method, and can realize the mass preparation of various nano transition metal borides.
The invention provides a preparation method of a nanometer transition metal boride, which comprises the following steps:
introducing boron-containing gas into the nano transition metal oxide or transition metal simple substance for boronizing, then introducing inert gas, and cooling to obtain the nano transition metal boride;
wherein the transition metal simple substance is prepared by reducing the nanometer transition metal oxide: and placing the nanometer transition metal oxide into a reactor, and introducing reducing gas for reduction to obtain the transition metal simple substance.
In the above preparation method, the nano transition metal oxide may be a supported nano transition metal oxide and/or a bulk nano transition metal oxide; the supported type is that the nanometer transition metal oxide is supported on a carrier, and the bulk type is that the nanometer transition metal oxide is not added with any carrier.
In the above preparation method, the preparation method of the supported nano transition metal oxide may specifically adopt at least one of isometric impregnation, hydrothermal synthesis, coprecipitation and chemical vapor deposition.
In the invention, the preparation of the nano transition metal oxide, specifically taking bulk nano iron oxide as an example, can be synthesized by the following method, and comprises the following steps:
(a) dissolving iron-containing water-soluble salt in deionized water to obtain a solution A, wherein the concentration of the solution A is 0.1-10 mol/L;
(b) putting the solution A into a water bath kettle, keeping the temperature at 25-90 ℃, adding a precipitator under the stirring condition, and controlling the dripping speed to keep the pH value of the solution at 6-10 to obtain precipitation slurry;
(c) stirring the precipitation slurry in a water bath, keeping the temperature at 25-90 ℃, aging for 0.1-10 h, carrying out suction filtration on the aged slurry, and washing with deionized water or absolute ethyl alcohol until the pH value of the filtrate is 6-8;
(d) and (3) putting the filter cake into an oven, drying for 2-40 h at 80-140 ℃, then putting into a muffle furnace, and roasting for 3-20 h at 300-600 ℃ to obtain the nano transition metal oxide.
In the preparation method of the bulk nano iron oxide, the iron-containing water-soluble salt may be at least one of ferric nitrate, ferric acetate, ferric sulfate and ferric chloride, and is preferably ferric nitrate;
(c) The medium pH may be 7.
In the above preparation method, the transition metal element in the nano transition metal oxide or the transition metal simple substance is at least one of yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, europium, titanium, zirconium, vanadium, niobium, molybdenum, tungsten, manganese, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum.
In the above production method, the reducing gas is reduced under the following conditions: heating to 180-1000 ℃ at a speed of 0.5-10 ℃/min; specifically, the temperature is raised to 300 ℃ and 280 ℃ at a rate of 10 ℃/min or to 280 ℃ to 300 ℃, 300 ℃ to 500 ℃, 200 ℃ to 400 ℃, or 200 ℃ to 500 ℃, or 5 ℃/min, from room temperature (25 ℃) to 200 ℃, and then from 200 ℃ to 400 ℃ or 900 ℃ at a rate of 1 ℃/min;
reducing at the constant temperature of 180-1000 ℃ for 0.5-20 h; specifically, the temperature can be kept constant at 300 ℃ for 6h, at 400 ℃ for 3h, at 280 ℃ for 12h, at 300 ℃ for 12h, at 900 ℃ for 3h, at 280-400 ℃ for 3-12 h, or at 280-900 ℃ for 3-12 h;
the reduction pressure can be 1-10 bar; specifically, the pressure may be 2bar, 1 to 2bar, 2 to 10bar or 1 to 7.5 bar.
In the above preparation method, the reducing gas is at least one of hydrogen, ammonia, carbon monoxide and hydrogen sulfide.
In the above preparation method, the reactor is a fixed bed and/or a circulating fluidized bed reactor.
In the preparation method, the flow rate of the introduced reducing gas is 50-500 mL/min, and specifically may be 200mL/min, 50-200 mL/min, 200-500 mL/min, 100-350 mL/min, 100-400 mL/min or 50-450 mL/min.
In the above preparation method, the flow rate of the boron-containing gas is 50 to 1000mL/min, specifically 50mL/min, 100mL/min, 410mL/min, 480mL/min, 500mL/min, 600mL/min, 800mL/min, 930mL/min or 50 to 930mL/min, specifically, for example, the hydrogen flow rate is 400mL/min + the boron trichloride flow rate is 80mL/min, the hydrogen flow rate is 400mL/min + boron trichloride flow rate is 100mL/min, the hydrogen flow rate is 500mL/min + trimethylboron flow rate is 100mL/min, the hydrogen flow rate is 900mL/min + boron trichloride flow rate is 30mL/min, the hydrogen flow rate is 750mL/min + boron trichloride flow rate is 50mL/min, and the hydrogen flow rate is 400mL/min + boron trichloride flow rate is 10 mL/min.
In the preparation method, the boronizing conditions are as follows: the temperature can be increased to 180-800 ℃ at a rate of 0.5-10 ℃/min, and specifically to 400 ℃, 450 ℃, 480 ℃ and 500 ℃ at a rate of 10 ℃/min;
The pressure can be 1-20 bar, specifically 2bar, 1-2 bar, 2-20 bar, 1-10 bar or 1-15 bar;
the time can be 0.5-80 h, specifically 3h, 6h, 10h, 72h, 3-6 h, 3-10 h, 6-10 h, 10-72 h or 3-72 h.
In the above production method, the boron-containing gas is a mixed gas of a boron source and the inert gas or the reducing gas.
In the above preparation method, the volume percentage concentration of the boron source in the boron-containing gas may be 0.01% to 100%, specifically 0.32%, 2.44%, 6.25%, 16.67%, 20%, 90%, or 0.03% to 90%;
the boron source is selected from at least one of trimethyl boron, triethyl boron, trimethoxy boron, boron trifluoride, boron trichloride, boron tribromide and boron triiodide.
In the above preparation method, the inert gas is at least one of helium, neon, nitrogen and argon.
The boron-containing gas is introduced by continuous aeration and/or pulse gas feeding.
The invention has the following advantages:
(1) the preparation temperature is low, and the size of the obtained transition metal boride can be controlled at a nanometer level;
(2) the product has high purity, and the phenomenon that a large amount of oxide is obtained by the traditional method is avoided;
(3) the method has strong applicability, and can be used for preparing various transition metal borides;
(4) Simple steps, good repeatability and mass preparation.
Drawings
FIG. 1 is an XRD spectrum of FeB of different sizes obtained in examples 2 and 3 of the present invention; wherein, a and b in fig. 1 are Co target XRD spectrograms of the FeB powder prepared in examples 2 and 3 of the present invention, respectively;
FIG. 2 shows Fe obtained in example 42XRD spectrogram of B;
FIG. 3 shows CoB and Co obtained in examples 6 and 7 of the present invention2B, wherein a and B in figure 3 are Co target XRD spectrums of the CoB powder prepared in the examples 6 and 7 of the invention respectively.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of Nano Metal oxide
484.82g of ferric nitrate nonahydrate are weighed and dissolved in deionized water to prepare a nitrate solution with the concentration of 1.5 mol/L; preparing an ammonia water solution with the concentration of 25-28 wt% into a solution with the concentration of about 6mol/L as a precipitator; dropwise adding a precipitator into a nitrate solution at the temperature of 80 ℃ and the pH value of 8.5-8.8 to obtain precipitation slurry; stirring and aging the precipitation slurry at 80 ℃ for 2 h; filtering, washing and spray-drying the aged slurry, wherein the air inlet temperature is controlled to be 180 ℃ and the air outlet temperature is controlled to be 90 ℃; and (3) roasting the dried spherical precursor at 450 ℃ for 5h to obtain the nano ferric oxide with the size of about 25 nm.
Other metal oxides (Mn)2O3，Co3O4NiO, CuO, etc.) can be prepared by a similar method, and the grain sizes of the metal oxides prepared by the method are all 15-50 nm.
Examples 2,
Weighing 10g of the nano ferric oxide obtained in the embodiment 1 of the invention, putting the nano ferric oxide into a quartz tube, carrying out temperature programming to 300 ℃ in a pure hydrogen atmosphere, keeping the temperature for 12 hours, and then naturally cooling to room temperature (25 ℃) in an argon atmosphere; wherein the heating rate is 10 ℃/min, and the reduction pressure is 2 bar; h2The flow rate of (2) is 200 mL/min.
Switching the reaction atmosphere into hydrogen and boron trichloride, raising the temperature to 400 ℃ by a program, keeping the temperature for 6 hours, and then naturally cooling to room temperature (25 ℃) in the hydrogen atmosphere; wherein the heating rate is 10 ℃/min and the pressure is 2 bar; the hydrogen flow is 400mL/min, and the boron trichloride flow is 10 mL/min.
And switching the reaction atmosphere to a passivation atmosphere, and ventilating at room temperature for 12h to obtain the FeB with the grain size of about 12 nm. Wherein the passivation atmosphere is 0.5% O299.5% Ar, flow 50 mL/min.
In fig. 1, a is a Co target XRD spectrum of the FeB powder prepared in this example, and it can be seen from the graph: the product obtained is a pure phase FeB with a grain size of about 12 nm.
Examples 3,
Weighing 10g of the nano ferric oxide obtained in the embodiment 1 of the invention, putting the nano ferric oxide into a quartz tube, carrying out temperature programming to 300 ℃ in a pure hydrogen atmosphere, keeping the temperature for 12 hours, and then naturally cooling to room temperature in an argon atmosphere; wherein the heating rate is 10 ℃/min, the pressure is 2bar, and H 2The flow rate of (2) is 200 mL/min.
Switching the reaction atmosphere into hydrogen and boron trichloride, raising the temperature to 500 ℃ by programming, keeping the temperature for 10 hours, and then naturally cooling to room temperature (25 ℃) in the hydrogen atmosphere; wherein the heating rate is 10 ℃/min, the pressure is 2bar, the hydrogen flow is 750mL/min, and the boron trichloride flow is 50 mL/min.
And switching the reaction atmosphere to a passivation atmosphere, and ventilating for 24 hours at room temperature to obtain the FeB. Wherein the passivation atmosphere is 0.5% O299.5% Ar, flow 50 mL/min.
Fig. 1 b is a Co target XRD spectrum of the FeB powder prepared in this example, which can be seen from the following chart: the product obtained is a pure phase FeB with a grain size of about 22 nm.
Examples 4,
Weighing 10g of the nano ferric oxide obtained in the embodiment 1 of the invention, putting the nano ferric oxide into a fixed bed reactor, carrying out programmed heating to 300 ℃ in a pure hydrogen atmosphere, keeping the temperature for 12 hours, and then naturally cooling to room temperature in an argon atmosphere; wherein the heating rate is 10 ℃/min, the pressure is 2bar, and H2The flow rate of (2) is 200 mL/min.
Switching the reaction atmosphere into hydrogen and boron trichloride, programming to 480 ℃, keeping the temperature for 6h, and then naturally cooling to room temperature (25 ℃) in the hydrogen atmosphere; wherein the heating rate is 10 ℃/min, the pressure is 2bar, the hydrogen flow is 900mL/min, the boron trichloride flow is 30mL/min, and Fe is obtained after the treatment 2B。
FIG. 2 shows Fe prepared in this example2The XRD spectrogram of the Co target of the B powder is as follows: the product obtained is phase-pure Fe2B, no other boride phases and B are found2O3Contamination of the phase, its grain size is about 26 nm.
Examples 5,
Weighing 10g of the nano ferric oxide obtained in the embodiment 1 of the invention, putting the nano ferric oxide into a quartz tube, carrying out temperature programming to 300 ℃ in a pure hydrogen atmosphere, keeping the temperature for 12 hours, and then naturally cooling to room temperature in an argon atmosphere; wherein the heating rate is 10 ℃/min, the pressure is 2bar, and H2The flow rate of (2) is 200 mL/min.
Switching the reaction atmosphere into hydrogen and trimethyl boron, raising the temperature to 400 ℃ by a program, keeping the temperature for 72h, and then naturally cooling to room temperature (25 ℃) in the hydrogen atmosphere; wherein the heating rate is 10 ℃/min, the pressure is 2bar, the hydrogen flow is 500mL/min, and the trimethyl boron flow is 100 mL/min.
And switching the reaction atmosphere to a passivation atmosphere, and ventilating for 12 hours at room temperature to obtain the FeB, wherein the grain size of the FeB is about 30 nm. Wherein the passivation atmosphere is 0.5% O299.5% Ar, flow 50 mL/min.
Examples 6,
Weighing 10g of the nano cobaltosic oxide obtained in the embodiment 1 of the invention, placing the nano cobaltosic oxide into a quartz tube, carrying out temperature programming to 280 ℃ in a pure hydrogen atmosphere, keeping the temperature for 12 hours, and then naturally cooling to room temperature in an argon atmosphere; wherein the heating rate is 10 ℃/min, the pressure is 2bar, H 2The flow rate of (2) is 200 mL/min.
Switching the reaction atmosphere into hydrogen and boron trichloride, raising the temperature to 400 ℃ by programming, keeping the temperature for 3 hours, and then naturally cooling to room temperature (25 ℃) in the hydrogen atmosphere; wherein the heating rate is 10 ℃/min, the pressure is 2bar, the hydrogen flow is 400mL/min, and the boron trichloride flow is 100 mL/min.
And switching the reaction atmosphere to a passivation atmosphere, and ventilating for 12 hours at room temperature to obtain the CoB. Wherein the passivation atmosphere is 0.5% O299.5% Ar, flow 50 mL/min.
Fig. 3 a is a Co target XRD spectrum of CoB powder prepared in this example, which can be seen from the graph: the product obtained was pure phase CoB, no other boride phases and B were found2O3Contamination of the phase, its grain size is about 15 nm.
Example 7,
Weighing 10g of cobaltosic oxide obtained in the embodiment 1 of the invention, placing the cobaltosic oxide into a quartz tube, carrying out temperature programming to 280 ℃ in a pure hydrogen atmosphere, keeping the temperature for 12 hours, and then naturally cooling to room temperature (25 ℃) in an argon atmosphere; wherein the heating rate is 10 ℃/min, the pressure is 2bar, and H2The flow rate of (2) is 200 mL/min.
Switching the reaction atmosphere into hydrogen and boron trichloride, raising the temperature to 450 ℃ by a program, keeping the temperature for 6h, and then naturally cooling to room temperature (25 ℃) in the hydrogen atmosphere; wherein the heating rate is 10 ℃/min, the pressure is 2bar, the hydrogen flow is 400mL/min, and the boron trichloride flow is 80 mL/min.
The reaction atmosphere is switched to passivation atmosphere, and ventilation is carried out for 12h at room temperature (25 ℃), thus obtaining Co and Co2The XRD spectrum of the mixed phase of B is shown as B in figure 3, and the size of the mixed phase is about 33 nm. Wherein the passivation atmosphere is 0.5% O299.5% Ar, flow 50 mL/min.
Example 8 preparation of Nano NiB
Weighing 10g of NiO powder, putting the NiO powder into a preparation reactor, and introducing 90% H2/10％BCl3The flow rate of the mixed gas (volume ratio) is 100mL/min, the temperature is increased from room temperature (25 ℃) to 200 ℃ at the speed of 5 ℃/min, then the temperature is increased from 200 ℃ to 400 ℃ at the speed of 1 ℃/min, the temperature is kept for 3H, and then the gas is switched to H2Naturally cooling to room temperature under the pressure of 2 bar; and switching the reaction atmosphere to a passivation atmosphere, and ventilating for 12 hours at room temperature to obtain the NiB. Wherein the passivation atmosphere is 0.5% O299.5% Ar, flow 50 mL/min.
Example 9 preparation of NanoMoB
Weighing 10g of ammonium molybdate tetrahydrate, and roasting in a muffle furnace at 500 ℃ for 3 hours; then put into a preparation reactor, and 90 percent of H is introduced2/10％BCl3The flow rate of the mixed gas (volume ratio) is 100mL/min, the temperature is increased from room temperature to 200 ℃ at the speed of 5 ℃/min, then the temperature is increased from 200 ℃ to 900 ℃ at the speed of 1 ℃/min, the temperature is kept for 3H, and then the gas is switched to H2Naturally cooling to room temperature; and switching the reaction atmosphere to a passivation atmosphere, and introducing air at room temperature for 12 hours at the pressure of 2bar to obtain the MoB. Wherein the passivation atmosphere is 0.5% O 299.5% Ar, flow 50 mL/min.
Claims (4)
1. A preparation method of nanometer transition metal boride comprises the following steps: introducing boron-containing gas into the nano transition metal oxide or transition metal simple substance for boronizing, then introducing inert gas, and cooling to obtain the nano transition metal boride;
wherein the transition metal simple substance is prepared by reducing the nanometer transition metal oxide: placing the nanometer transition metal oxide into a reactor, and introducing reducing gas for reduction to obtain the transition metal simple substance;
the transition metal element in the nanometer transition metal oxide or the transition metal simple substance is at least one of molybdenum, tungsten, manganese, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum;
the reducing gas is at least one of hydrogen, ammonia, carbon monoxide and hydrogen sulfide;
the reducing gas reduction conditions are as follows: heating to 280-1000 ℃ at the speed of 5-10 ℃/min;
reducing at the constant temperature of 280-1000 ℃ for 12-20 h; the reduction pressure is 2-10 bar;
introducing the reducing gas at a flow rate of 50-500 mL/min;
the flow rate of the introduced boron-containing gas is 50-1000 mL/min;
the boronation conditions were as follows: the temperature is 400-800 ℃; the pressure is 2-20 bar;
The time is 3-80 h;
the boron-containing gas is a mixed gas of a boron source and the inert gas or the reducing gas;
the volume percentage concentration of the boron source in the boron-containing gas is 0.01-100%;
the boron source is selected from at least one of trimethyl boron, triethyl boron, trimethoxy boron, boron trifluoride, boron trichloride, boron tribromide and boron triiodide.
2. The method of claim 1, wherein: the nano transition metal oxide is a supported nano transition metal oxide and/or a bulk nano transition metal oxide; the supported type is that the nanometer transition metal oxide is supported on a carrier, and the bulk type is that no carrier is added to the nanometer transition metal oxide;
the preparation method of the supported nano transition metal oxide specifically adopts at least one of isometric impregnation, hydrothermal synthesis, coprecipitation and chemical vapor deposition.
3. The method of claim 1, wherein: the reactor is a fixed bed and/or a circulating fluidized bed reactor.
4. The method of claim 1, wherein: the inert gas is at least one of helium, neon, nitrogen and argon;
The boron-containing gas is introduced by continuous aeration and/or pulse gas feeding.
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