CN113307246B - Carbon-loaded transition metal/transition metal nitride composite material and preparation method thereof - Google Patents
Carbon-loaded transition metal/transition metal nitride composite material and preparation method thereof Download PDFInfo
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- CN113307246B CN113307246B CN202110646792.XA CN202110646792A CN113307246B CN 113307246 B CN113307246 B CN 113307246B CN 202110646792 A CN202110646792 A CN 202110646792A CN 113307246 B CN113307246 B CN 113307246B
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- C01B32/00—Carbon; Compounds thereof
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- C01B21/00—Nitrogen; Compounds thereof
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Abstract
The invention discloses a carbon-loaded carbon materialTransition metal/transition metal nitride composite material and preparation method, the preparation method includes the following steps: 1) under protective atmosphere, heating and melting cyanamide to form a clear transparent solution, and continuously stirring in the melting process; 2) completely dissolving metal salt in the cyanamide solution obtained in the step 1) to obtain a mixed solution; 3) adding NaHCO to the mixed solution3Stirring, changing color of the solution, separating out precipitate, continuously stirring until the reaction is complete, and cooling to room temperature to obtain a solid mixture containing hydrogen cyanate; 4) and cleaning and drying the solid mixture, then carrying out heat treatment, and cooling to room temperature to obtain the carbon-supported transition metal/transition metal nitride composite material. The composite material obtained by the method has the characteristics of high purity, good crystallinity, high yield, large specific surface area, controllable structural unit, good stability and the like, and can be used for battery electrodes, catalysts, semiconductors and the like.
Description
Technical Field
The invention belongs to the technical field of nitride material preparation, and particularly relates to a carbon-supported transition metal/transition metal nitride composite material and a preparation method thereof.
Background
Transition Metal Nitrides (TMNs) are a class of intermetallic gap compounds in which nitrogen is incorporated into Transition metals, generally having the advantages of high conductivity, high corrosion resistance, high melting point, etc., and having a unique d-charged electronic structure. Transition Metal (TM) has a vacant d-orbital that can be used for bonding and a high charge/radius ratio, and it is easy to form stable complex compounds with various ligands. These characteristics make the heterogeneous material TM/TMNs can be used as potential high-performance energy storage electrode material high-activity electrocatalyst. In general, the current methods for synthesizing TM/TMNs can be briefly summarized as physical methods and chemical methods. Physical methods include sputtering, laser ablation, and arc discharge, among others. Sputtering is most commonly used because of its high deposition rate. The method requires sputtering gas (argon) and reaction gas (nitrogen), and prepares a high-purity film with controllable stoichiometry and composition by physical vapor depositionAnd (3) sampling. For example, Murthy et al prepared Ag-Mo using magnetron co-sputtering technique3N2、V-Mo3N2And Cu-Mo3N2A series of molybdenum nitride films (Murthy A.P.; et al. electrochim. acta 2018,283,1525). The chemical method comprises reacting a metal precursor at NH3Medium-high temperature annealing, high-temperature ammonolysis of metal chlorides, solvothermal treatment and the like. For example, Wang et al use hydrazine reduction (NH)4)6Mo7O24Solution preparation of Fe-containing amorphous MoO2Amorphous Fe-MoO2NH at 400 DEG C3Fe-Mo converted to face-centered cubic in atmosphere2N, and hexagonal Fe-MoN is produced at 600 ℃ (Wang H.M.; et al.J.solid State chem.2012,194, 238.); yao et al grow layered double hydroxide on carbon cloth, and then use urea as nitrogen source to calcine to obtain X-Co4N/CC (X ═ Cr, Fe, Mn, Mo) (Yao N.; et al.adv.energy mater.2019, 1902449); guan et al first synthesizes a two-dimensional Co-ZIF-L structure by using a liquid phase method, and then obtains Co/CoN by carbonization and thermal ammonia reductionxNitrogen-doped carbon nanoarrays of nanoparticles (Guan C.; et al.J. energy Storage mater.2019,16,243.).
However, the physical synthesis method of most of the TM/TMNs at present has harsh conditions, slow synthesis process and complex operation, and is not suitable for general synthesis. Most chemical methods involve the use of toxic nitrogen sources, are not very environmentally friendly and are inefficient. Therefore, there is an urgent need to develop an environmentally friendly, low-cost and efficient method for synthesizing TMNs.
Disclosure of Invention
The present invention aims to provide a carbon-supported transition metal/transition metal nitride composite material and a preparation method thereof, aiming at the defects existing in the prior method. The invention firstly utilizes the cheap cyanamide, the sodium bicarbonate and the metal precursor (namely the metal salt) to prepare the corresponding hydrogen cyanate, and then the corresponding carbon-supported transition metal/transition metal nitride composite material can be obtained by further heat treatment of the hydrogen cyanate. The method does not need toxic and harmful ammonia gas in the conventional process, has simple experimental process, and accords with the green chemical development concept.
The invention adopts the following specific technical scheme:
in a first aspect, the present invention provides a method for preparing a carbon-supported transition metal/transition metal nitride composite material, comprising the steps of:
1) under protective atmosphere, heating and melting cyanamide to form a clear transparent solution, and continuously stirring in the melting process;
2) completely dissolving metal salt in the cyanamide solution obtained in the step 1) to obtain a mixed solution;
3) adding NaHCO to the mixed solution3Stirring, changing color of the solution, separating out precipitate, continuously stirring until the reaction is complete, and cooling to room temperature to obtain a solid mixture containing hydrogen cyanate;
4) and cleaning and drying the solid mixture, then carrying out heat treatment, and cooling to room temperature to obtain the carbon-supported transition metal/transition metal nitride composite material.
Preferably, the protective atmosphere in step 1) is nitrogen, argon or a mixed gas of the two.
Preferably, the heating temperature in the step 1) is 50-100 ℃.
Preferably, the metal salt comprises one or more of copper chloride, nickel nitrate, cobalt acetate and ferrous sulfate.
Preferably, in the step 2), the molar ratio of the metal salt to the cyanamide is 1: 10-1: 100.
further, in the step 3), NaHCO3And the molar ratio of the metal ions in the mixed solution is 1.5: 1-20: 1.
preferably, in the step 4), the solid mixture is dispersed in water, and the precipitate is collected by centrifugation, followed by washing with water and ethanol, and repeated several times to achieve washing of the solid mixture.
Preferably, the heat treatment is specifically as follows:
in an inert atmosphere, heating the cleaned and dried solid mixture to 300-700 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 0.5-10 h, and cooling to room temperature.
Further, the inert atmosphere is nitrogen or argon.
In a second aspect, the invention provides a carbon-supported transition metal/transition metal nitride composite material prepared by the preparation method of any one of the first aspect, wherein the carbon-supported transition metal/transition metal nitride composite material is a nano/submicron particle aggregate with the size of 100-500 nm.
Compared with the prior art, the invention has the following beneficial effects:
the components of the carbon-supported transition metal/transition metal nitride composite material prepared by the preparation method comprise a transition metal simple substance and a transition metal nitride, and the general formula can be expressed as M/MxNyWherein, M represents a metal element and can be any one or combination of Fe, Co, Ni and Cu in any proportion (specifically determined according to the added metal source); n is nitrogen element; x and y are stoichiometric numbers of metal and nitrogen elements; c is carbon element. The composite material obtained by the method is an aggregate of nano/submicron particles with the size of 100-500 nm, has the characteristics of high purity, good crystallinity, high yield, large specific surface area, controllable structural units, good stability and the like, and can be used for battery electrodes, catalysts, semiconductors and the like.
Drawings
FIG. 1 is a scanning electron microscope photograph of carbon-supported copper/copper nitride prepared in example 1;
FIG. 2 is an XRD ray diffraction pattern of copper on carbon/copper nitride as prepared in example 1;
FIG. 3 is an XRD ray diffraction pattern of nickel on carbon/nickel nitride as prepared in example 2;
FIG. 4 is a scanning electron microscope photograph of the carbon-supported cobalt/cobalt nitride prepared in example 3;
figure 5 is an XRD ray diffraction pattern of the carbon-supported iron/iron nitride prepared in example 4.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
Example 1
1) In N20.630g of cyanamide was heated to 50 ℃ under a protective atmosphere and melted completely to form a clear, transparent solution, with vigorous stirring being continued during the melting.
2) 0.1350g of copper chloride (CuCl)2) Adding into the molten cyanamide solution, and continuously stirring until the solution turns into dark green to obtain a mixed solution.
3) 0.168g NaHCO3Slowly adding the mixture into the dark green solution to immediately turn black and precipitate, and continuously stirring until the reaction is complete. After the reaction, the mixed solution was cooled to room temperature to obtain a solution containing Cu (NCN)2The solid mixture of (1).
4) Dispersing the solid mixture into water, centrifuging to collect black precipitate, washing with distilled water and ethanol for three times, and drying at 60 deg.C under vacuum for 12 hr to obtain Cu (NCN)2。
5) Mixing the obtained Cu (NCN)2Carrying out heat treatment, wherein the heat treatment process comprises the following steps: in N2Heating to 350 ℃ at the speed of 5 ℃/min in the atmosphere, preserving heat for 2h, cooling to room temperature along with the furnace, and taking out to obtain Cu/Cu3N/C composite material.
Cu/Cu prepared in this example3The scanning electron microscope picture of N/C is shown in FIG. 1, from which it can be seen that Cu/Cu3The shape of the N/C is a sea urchin-shaped spherical block body formed by aggregating nano particles, and the size of the N/C is 300-500 nm. Cu/Cu3The XRD ray diffraction pattern of N/C is shown in FIG. 2, and the position of the diffraction peak can be seen together with standard card PDF 47-1088 (Cu)3N) and PDF 04-0836(Cu) are consistent in reported results, and the phase of the product can be judged to be Cu/Cu3N/C. Therefore, the phase of copper nitride in the composite material prepared in the embodiment is Cu3And N is a sea urchin-shaped large particle formed by connecting small particles with the particle size of 20-50 nm into particles with the particle size of 300-500 nm.
Example 2
1) 2.10g of cyanamide are heated to 60 ℃ under Ar protective atmosphere and melted completely to form a clear, transparent solution, with continuous vigorous stirring during the melting.
2) 0.366g of nickel nitrate (Ni (NO)3)2) Adding into the molten cyanamide solution, and continuously stirring until the solution turns into grey brown to obtain a mixed solution.
3) 0.420g NaHCO3Slowly adding the mixture into the mixture to ensure that the gray brown solution immediately turns into cyan and precipitates, and continuously stirring until the reaction is complete. After the reaction, the mixed solution was cooled to room temperature to obtain a solution containing Ni (HNCN)2The solid mixture of (1).
4) Dispersing the solid mixture into water, centrifuging to collect greenish precipitate, washing with distilled water and ethanol for three times, and drying at 60 deg.C under vacuum for 12 hr to obtain Ni (HNCN)2。
5) Mixing the obtained Ni (HNCN)2Carrying out heat treatment, wherein the heat treatment process comprises the following steps: in N2Heating to 475 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 5h, cooling to room temperature along with the furnace, and taking out to obtain Ni/Ni3N/C composite material.
Ni/Ni prepared in this example3The XRD ray diffraction pattern of N/C is shown in FIG. 3, and the position of the diffraction peak can be seen together with standard card PDF 10-0280 (Ni)3N) and PDF 04-0850(Ni), and the phase of the product obtained in this example was determined to be Ni/Ni3N/C。
Example 3
1) In N24.20g of cyanamide are heated to 80 ℃ under a protective atmosphere of/Ar mixture, melted completely to form a clear, transparent solution, and stirred vigorously during the melting.
2) 0.177g of cobalt acetate (Co (CH)3COO)2) Adding into the molten cyanamide solution, and continuously stirring until the solution turns into light blue to obtain a mixed solution.
3) 0.420g NaHCO3Slowly adding into the mixed solution to make the light blue solution turn into pink purple instantly,immediately precipitate out, and continue stirring until the reaction is complete. After the reaction, the mixed solution was cooled to room temperature to obtain a mixture containing Co (HNCN)2The solid mixture of (1).
4) Dispersing the mixture into water, centrifuging to collect pink purple precipitate, washing with distilled water and ethanol for three times, and drying at 60 deg.C under vacuum for 12 hr to obtain Co (HNCN)2。
5) Mixing the obtained Co (HNCN)2Carrying out heat treatment, wherein the heat treatment process comprises the following steps: in N2Heating to 600 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 5 hours, cooling to room temperature along with the furnace, and taking out to obtain Co/Co3N/C composite material.
The phase of the cobalt nitride prepared in this example is Co3And the SEM photograph of the N is shown in FIG. 4, and the appearance of the N is a larger block formed by the agglomeration of nano particles of 300-400 nm.
Example 4
1) 0.420g of cyanamide was heated to 70 ℃ under Ar protective atmosphere and melted completely to form a clear transparent solution, with vigorous stirring being continued during the melting.
2) 0.152g of ferrous sulfate (Fe (SO)4) Add to the above molten cyanamide solution, and keep stirring until the solution turns into greenish black to obtain a mixed solution.
3) 0.168g NaHCO3Slowly adding the mixture into the mixed solution, immediately changing the dark green solution into light green, immediately precipitating, and continuously stirring until the reaction is complete. After the reaction, the mixed solution was cooled to room temperature to obtain a solution containing Fe (HNCN)2The solid mixture of (1).
4) Dispersing the solid mixture into water, centrifuging to collect light green precipitate, washing with distilled water and ethanol for three times, and drying at 60 deg.C under vacuum for 12 hr to obtain Fe (HNCN)2。
5) The resulting Fe (HNCN)2Carrying out heat treatment, wherein the heat treatment process comprises the following steps: in N2Heating to 700 deg.C at a rate of 10 deg.C/min in atmosphere, holding for 8 hr, and cooling to room temperatureTaking out to obtain Fe/Fe3N/C composite material.
The phase of the iron nitride prepared in this example is Fe3N, the XRD diffraction pattern is shown in figure 5, and the position of the diffraction peak is similar to that of PDF 49-1644 (Fe) of standard card3The results reported by N) and PDF 06-0696(Fe) are consistent, and the phase of the product can be judged to be Fe/Fe3N/C。
Example 5
1) In N2Under a protective atmosphere, 2.520g of cyanamide are heated to 100 ℃ and melted completely to form a clear and transparent solution, with continuous vigorous stirring during the melting.
2) 0.131g of nickel sulfate hexahydrate and 0.228 g of ferrous sulfate (FeSO)4) Adding into the molten cyanamide solution, and stirring until the solution turns into light yellow to obtain a mixed solution.
3) 0.420g NaHCO3Slowly adding the mixture into the light yellow solution to immediately turn into black brown, immediately precipitating out, and continuously stirring until the reaction is complete. After the reaction is finished, cooling the mixed solution to room temperature to obtain the Ni-containing alloy0.25Fe0.75(HNCN)2The solid mixture of (1).
4) Dispersing the solid mixture into water, collecting black brown precipitate by centrifugation, washing with distilled water and ethanol for three times, and drying at 60 deg.C under vacuum for 12 hr to obtain Ni0.25Fe0.75(HNCN)2。
5) The obtained Ni0.25Fe0.75(HNCN)2Carrying out heat treatment, wherein the heat treatment process comprises the following steps: in N2Heating to 650 ℃ at the speed of 20 ℃/min in the atmosphere, preserving heat for 8h, cooling to room temperature along with the furnace, and taking out to obtain Fe/NiFe3N/C composite material.
It can be known from the characterization that the transition metal simple substance prepared in this example is Fe, and the phase of the binary nickel iron nitride is NiFe3N。
According to the embodiment, in the high-temperature treatment process, the carbon-rich and nitrogen-rich precursor hydrogen cyanate is subjected to in-situ decomposition, a part of metal elements and nitrogen elements are combined and converted into metal nitrides, and the other part of metal elements are subjected to carbothermic reduction into simple substances, so that the components of the composite material comprise the transition metal simple substances and the transition metal nitrides. The invention utilizes cheap cyanamide, sodium bicarbonate and metal precursor (namely metal salt) to prepare corresponding hydrogen cyanate, and then the corresponding carbon-supported transition metal/transition metal nitride composite material can be obtained by further heat treatment of the hydrogen cyanate.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (8)
1. A preparation method of a carbon-supported transition metal/transition metal nitride composite material is characterized by comprising the following steps:
1) under protective atmosphere, heating and melting cyanamide to form a clear transparent solution, and continuously stirring in the melting process; the heating temperature is 50-100 ℃;
2) completely dissolving metal salt in the cyanamide solution obtained in the step 1) to obtain a mixed solution; the molar ratio of the metal salt to the cyanamide is 1: 10-1: 100, respectively;
3) adding NaHCO to the mixed solution3Stirring, changing color of the solution, separating out precipitate, continuously stirring until the reaction is complete, and cooling to room temperature to obtain a solid mixture containing hydrogen cyanate;
4) and cleaning and drying the solid mixture, then carrying out heat treatment, and cooling to room temperature to obtain the carbon-supported transition metal/transition metal nitride composite material.
2. The method for preparing a carbon-supported transition metal/transition metal nitride composite material according to claim 1, wherein the protective atmosphere in the step 1) is nitrogen, argon or a mixed gas of the nitrogen and the argon.
3. The method for preparing a carbon-supported transition metal/transition metal nitride composite material according to claim 1, wherein the metal salt comprises one or more of copper chloride, nickel nitrate, cobalt acetate, and ferrous sulfate.
4. The method for preparing a carbon-supported transition metal/transition metal nitride composite material according to claim 1, wherein in the step 3), NaHCO is used3And the molar ratio of the metal ions in the mixed solution is 1.5: 1-20: 1.
5. the method for preparing a carbon-supported transition metal/transition metal nitride composite material according to claim 1, wherein in the step 4), the solid mixture is dispersed in water, and the precipitate is collected by centrifugation, followed by washing with water and ethanol, and repeating a plurality of times to effect washing of the solid mixture.
6. The method for preparing a carbon-supported transition metal/transition metal nitride composite material according to claim 1, wherein the heat treatment is specifically as follows:
in an inert atmosphere, heating the cleaned and dried solid mixture to 300-700 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 0.5-10 h, and cooling to room temperature.
7. The method of preparing a carbon-supported transition metal/transition metal nitride composite according to claim 6, wherein the inert atmosphere is nitrogen or argon.
8. The carbon-supported transition metal/transition metal nitride composite material prepared by the preparation method of any one of claims 1 to 7, wherein the carbon-supported transition metal/transition metal nitride composite material is a nano/submicron particle aggregate with a size of 100 to 500 nm.
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