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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- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical class [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 1
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- 238000000608 laser ablation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
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- 238000004729 solvothermal method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
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Abstract
本发明公开一种碳负载过渡金属/过渡金属氮化物复合材料及制备方法，制备方法包含以下步骤：1)在保护性气氛下，将氨基氰加热熔化至形成澄清透明溶液，熔化过程中持续搅拌；2)将金属盐完全溶解于步骤1)所得氨基氰溶液中，得到混合溶液；3)向所述混合溶液中加入NaHCO3并搅拌，溶液变色并有沉淀物析出，继续搅拌至反应完全，冷却至室温后，得到含氢氰酸盐的固体混合物；4)将所述固体混合物清洗干燥后进行热处理，冷却至室温后得到碳负载过渡金属/过渡金属氮化物复合材料。通过本发明方法得到的复合材料纯度高、结晶性好、产率高，具有比表面积大、结构单元可控、稳定性良好等特性，可用于电池电极、催化剂、半导体等方面。
The invention discloses a carbon-supported transition metal/transition metal nitride composite material and a preparation method. The preparation method comprises the following steps: 1) under a protective atmosphere, heating and melting cyanamide to form a clear and transparent solution, and continuously stirring during the melting process 2) The metal salt is completely dissolved in the cyanamide solution obtained in step 1) to obtain a mixed solution; 3 ) NaHCO is added to the mixed solution and stirred, the solution changes color and precipitates out, and continues to stir until the reaction is complete, After cooling to room temperature, a solid mixture containing hydrocyanate is obtained; 4) the solid mixture is washed and dried, and then heat-treated, and after cooling to room temperature, a carbon-supported transition metal/transition metal nitride composite material is obtained. The composite material obtained by the method of the invention has the characteristics of high purity, good crystallinity, high yield, large specific surface area, controllable structural unit and good stability, and can be used in battery electrodes, catalysts, semiconductors and the like.
Description
技术领域technical field
本发明属于氮化物材料制备技术领域，具体涉及一种碳负载过渡金属/过渡金属氮化物复合材料及制备方法。The invention belongs to the technical field of nitride material preparation, in particular to a carbon-supported transition metal/transition metal nitride composite material and a preparation method.
背景技术Background technique
过渡金属氮化物(Transition metal nitrides，TMNs)是氮元素键入到过渡金属中的一类金属间隙化合物，通常具有高导电性、高耐腐蚀性、高熔点等优势,且具有独特的d带电子结构。过渡金属单质(Transition metal，TM)具有能用于成键的空d轨道以及较高的电荷/半径比，都很容易与各种配位体形成稳定的配位化合物。这些特点使得异质材料TM/TMNs可以作为潜在的高性能储能电极材料高活性电催化剂或来使用。一般而言，当前TM/TMNs的合成方法可以简单的概括为物理方法和化学方法。物理方法包括溅射、激光烧蚀和电弧放电等。溅射法因其高沉积速率最为常用。该方法需要溅射气体(氩气)和反应气体(氮气)，通过物理气相沉积制备出具有可控化学计量和成分的高纯度薄膜样品。例如，Murthy等采用磁控共溅射技术制备了Ag-Mo3N2、V-Mo3N2和Cu-Mo3N2等一系列氮化钼薄膜(MurthyA.P.；et al.Electrochim.Acta 2018,283,1525)。化学方法则包含将金属前体在NH3中高温退火、高温氨解金属氯化物和溶剂热等。例如，Wang等采用联氨还原(NH4)6Mo7O24溶液制备了含Fe的无定形MoO2，非晶态Fe-MoO2在400℃下NH3气氛中转化为面心立方的Fe-Mo2N，而在600℃下生成六方Fe-MoN(Wang H.M.；et al.J.Solid State Chem.2012,194,238.)；Yao等在碳布上生长层状双金属氢氧化物，而后再以尿素为氮源，煅烧得到X-Co4N/CC(X＝Cr,Fe,Mn,Mo)(Yao N.；et al.Adv.Energy Mater.2019,1902449)；Guan等先利用液相法合成了二维Co-ZIF-L结构，而后经碳化、热氨还原，得到了Co/CoNx纳米颗粒的氮掺杂碳纳米阵列(Guan C.；et al.J.Energy Storage Mater.2019,16,243.)。Transition metal nitrides (TMNs) are a class of metal interstitial compounds in which nitrogen is keyed into transition metals. They usually have the advantages of high electrical conductivity, high corrosion resistance, high melting point, etc., and have a unique d-band electronic structure. . Transition metals (TM) have vacant d orbitals that can be used for bonding and high charge/radius ratios, so they can easily form stable coordination compounds with various ligands. These characteristics make the heterogeneous materials TM/TMNs can be used as potential high-performance electrocatalysts for high-performance energy storage electrodes or highly active electrocatalysts. In general, the current synthesis methods of TM/TMNs can be simply summarized as physical methods and chemical methods. Physical methods include sputtering, laser ablation, and arc discharge. The sputtering method is most commonly used because of its high deposition rate. The method requires sputtering gas (argon) and reactive gas (nitrogen) to prepare high-purity thin film samples with controllable stoichiometry and composition by physical vapor deposition. For example, Murthy et al. prepared a series of molybdenum nitride films such as Ag-Mo 3 N 2 , V-Mo 3 N 2 and Cu-Mo 3 N 2 by magnetron co-sputtering (Murthy A.P.; et al. Electrochim). .Acta 2018, 283, 1525). Chemical methods include high temperature annealing of metal precursors in NH3 , high temperature ammonolysis of metal chlorides, and solvothermal methods. For example, Wang et al. prepared Fe-containing amorphous MoO 2 by reducing (NH 4 ) 6 Mo 7 O 24 solution with hydrazine, and the amorphous Fe-MoO 2 was converted to face-centered cubic Fe at 400 °C in an NH 3 atmosphere. -Mo 2 N, while hexagonal Fe-MoN was formed at 600 °C (Wang HM; et al. J. Solid State Chem. 2012, 194, 238.); Yao et al. grew layered double metal hydroxides on carbon cloth, and then Then, using urea as the nitrogen source, calcination obtains X-Co 4 N/CC (X=Cr, Fe, Mn, Mo) (Yao N.; et al. Adv. Energy Mater. 2019, 1902449); Guan et al. The two-dimensional Co-ZIF-L structure was synthesized by phase method, and then carbonized and thermally reduced by ammonia to obtain nitrogen-doped carbon nanoarrays of Co/CoN x nanoparticles (Guan C.; et al.J. Energy Storage Mater. 2019, 16, 243.).
然而，目前大部分TM/TMNs的物理合成方法的条件较为苛刻，合成过程缓慢且操作复杂，不适用于一般合成。而多数化学方法均涉及有毒氮源的使用，对环境十分不友好且效率较低。因此，迫切需要开发环境友好、低成本且高效的TMNs合成方法。However, most of the physical synthesis methods of TM/TMNs currently have harsh conditions, slow synthesis process and complicated operations, which are not suitable for general synthesis. However, most chemical methods involve the use of toxic nitrogen sources, which are very unfriendly to the environment and have low efficiency. Therefore, there is an urgent need to develop environmentally friendly, low-cost, and efficient TMNs synthesis methods.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于针对上述现有方法中存在的不足，提供一种碳负载过渡金属/过渡金属氮化物复合材料及制备方法。本发明首先利用廉价的氨基氰、碳酸氢钠和金属前体(即金属盐)制备出相应的氢氰酸盐，而后通过对氢氰酸盐进一步的热处理即可得到相应的碳负载过渡金属/过渡金属氮化物复合材料。本发明无需使用常规工艺中有毒有害的氨气，实验过程简单，符合绿色化学发展理念。The purpose of the present invention is to provide a carbon-supported transition metal/transition metal nitride composite material and a preparation method for the deficiencies existing in the above-mentioned existing methods. The invention firstly utilizes cheap cyanamide, sodium bicarbonate and metal precursors (that is, metal salts) to prepare the corresponding hydrogen cyanate, and then further heat treatment of the hydrogen cyanate can obtain the corresponding carbon-supported transition metal/ Transition metal nitride composites. The invention does not need to use toxic and harmful ammonia gas in the conventional process, the experiment process is simple, and conforms to the development concept of green chemistry.
本发明所采用的具体技术方案如下：The concrete technical scheme adopted in the present invention is as follows:
第一方面，本发明提供了一种碳负载过渡金属/过渡金属氮化物复合材料的制备方法，包含以下步骤：In a first aspect, the present invention provides a method for preparing a carbon-supported transition metal/transition metal nitride composite material, comprising the following steps:
1)在保护性气氛下，将氨基氰加热熔化至形成澄清透明溶液，熔化过程中持续搅拌；1) Under the protective atmosphere, the cyanamide is heated and melted to form a clear and transparent solution, and the stirring is continued during the melting process;
2)将金属盐完全溶解于步骤1)所得氨基氰溶液中，得到混合溶液；2) completely dissolving the metal salt in the cyanamide solution obtained in step 1) to obtain a mixed solution;
3)向所述混合溶液中加入NaHCO3并搅拌，溶液变色并有沉淀物析出，继续搅拌至反应完全，冷却至室温后，得到含氢氰酸盐的固体混合物； 3 ) adding NaHCO to the mixed solution and stirring, the solution changes color and precipitates out, continue to stir until the reaction is complete, and after cooling to room temperature, obtain a solid mixture containing hydrocyanate;
4)将所述固体混合物清洗干燥后进行热处理，冷却至室温后得到碳负载过渡金属/过渡金属氮化物复合材料。4) After cleaning and drying the solid mixture, heat treatment is performed, and after cooling to room temperature, a carbon-supported transition metal/transition metal nitride composite material is obtained.
作为优选，所述步骤1)中的保护性气氛为氮气、氩气或两者的混合气体。Preferably, the protective atmosphere in the step 1) is nitrogen, argon or a mixture of the two.
作为优选，所述步骤1)中加热温度为50～100℃。Preferably, the heating temperature in the step 1) is 50-100°C.
作为优选，所述金属盐包括氯化铜、硝酸镍、乙酸钴、硫酸亚铁中的一种或几种。Preferably, the metal salt includes one or more of copper chloride, nickel nitrate, cobalt acetate, and ferrous sulfate.
作为优选，所述步骤2)中，金属盐与氨基氰的摩尔比为1：10～1：100。Preferably, in the step 2), the molar ratio of the metal salt to the cyanamide is 1:10-1:100.
进一步的，所述步骤3)中，NaHCO3和混合溶液中金属离子的摩尔比为1.5：1～20：1。Further, in the step 3), the molar ratio of NaHCO 3 and metal ions in the mixed solution is 1.5:1 to 20:1.
作为优选，所述步骤4)中，将固体混合物分散在水中，并离心收集沉淀物，随后用水和乙醇洗涤，重复多次以实现固体混合物的清洗。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 the cleaning of the solid mixture.
作为优选，所述热处理具体如下：Preferably, the heat treatment is as follows:
在惰性气氛中，将清洗干燥后的固体混合物以1～20℃/min的升温速率加热到300～700℃，保温0.5～10h之后冷却至室温。In an inert atmosphere, the washed and dried solid mixture is heated to 300 to 700° C. at a heating rate of 1 to 20° C./min, kept for 0.5 to 10 hours, and then cooled to room temperature.
进一步的，所述惰性气氛为氮气或氩气。Further, the inert atmosphere is nitrogen or argon.
第二方面，本发明提供了一种利用第一方面任一所述制备方法制得的碳负载过渡金属/过渡金属氮化物复合材料，其中，碳负载过渡金属/过渡金属氮化物复合材料为100～500nm尺寸的纳米/亚微米颗粒团聚体。In a second aspect, the present invention provides a carbon-supported transition metal/transition metal nitride composite material prepared by any of the preparation methods described in the first aspect, wherein the carbon-supported transition metal/transition metal nitride composite material is 100 -500nm size nano/submicron particle agglomerates.
本发明相对于现有技术而言，具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
通过本发明制备方法制备得到的碳负载过渡金属/过渡金属氮化物复合材料，其成分包括过渡金属单质和过渡金属氮化物，通式可表示为M/MxNy/C，其中，M表示金属元素，可以为Fe、Co、Ni、Cu中的任意一种或数种的任意比例组合(具体对应于添加的金属源而定)；N为氮元素；x和y为金属与氮元素的化学计量数；C为碳元素。通过本发明方法得到的复合材料为尺寸在100～500nm之间的纳米/亚微米颗粒的团聚体，且纯度高、结晶性好、产率高，具有比表面积大、结构单元可控、稳定性良好等特性，可用于电池电极、催化剂、半导体等方面。The carbon-supported transition metal/transition metal nitride composite material prepared by the preparation method of the present invention includes transition metal element and transition metal nitride, and the general formula can be expressed as M/M x N y /C, wherein M represents Metal element, which can be any one of Fe, Co, Ni, and Cu in any proportion or combination (specifically corresponding to the added metal source); N is nitrogen element; x and y are metal and nitrogen element. Stoichiometric number; C is carbon. The composite material obtained by the method of the present invention is an agglomerate of nano/submicron particles with a size between 100 and 500 nm, and has high purity, good crystallinity, high yield, large specific surface area, controllable structural unit and stability. It has good characteristics and can be used in battery electrodes, catalysts, semiconductors, etc.
附图说明Description of drawings
图1为实施例1中所制备的碳负载铜/氮化铜的扫描电子显微镜图；1 is a scanning electron microscope image of carbon-supported copper/copper nitride prepared in Example 1;
图2为实施例1中所制备的碳负载铜/氮化铜的XRD射线衍射图；Fig. 2 is the XRD ray diffractogram of carbon-supported copper/copper nitride prepared in Example 1;
图3为实施例2中所制备的碳负载镍/氮化镍的XRD射线衍射图；3 is the XRD ray diffractogram of carbon-supported nickel/nickel nitride prepared in Example 2;
图4为实施例3中所制备的碳负载钴/氮化钴的扫描电子显微镜图；4 is a scanning electron microscope image of carbon-supported cobalt/cobalt nitride prepared in Example 3;
图5为实施例4中所制备的碳负载铁/氮化铁的XRD射线衍射图。FIG. 5 is the XRD pattern of the carbon-supported iron/iron nitride prepared in Example 4. FIG.
具体实施方式Detailed ways
下面结合附图和具体实施方式对本发明做进一步阐述和说明。本发明中各个实施方式的技术特征在没有相互冲突的前提下，均可进行相应组合。The present invention will be further elaborated and described below with reference to the accompanying drawings and specific embodiments. The technical features of the various embodiments of the present invention can be combined correspondingly on the premise that there is no conflict with each other.
实施例1Example 1
1)在N2保护性气氛下，将0.630g氨基氰加热至50℃，熔化完全至形成澄清透明溶液，在熔化过程中持续剧烈搅拌。1) Under a N2 protective atmosphere, heat 0.630 g of cyanamide to 50 °C, melt completely until a clear and transparent solution is formed, and continue to stir vigorously during the melting process.
2)将0.1350g氯化铜(CuCl2)加至上述熔融态氨基氰溶液中，继续保持搅拌至溶液变成深绿色，得到混合溶液。2) Add 0.1350 g of copper chloride (CuCl 2 ) to the above molten cyanamide solution, and continue to keep stirring until the solution turns dark green to obtain a mixed solution.
3)将0.168g NaHCO3缓慢加入上述混合溶液中，深绿色的溶液立刻变成黑色，并立即有沉淀析出，继续搅拌至反应完全。反应结束后，将上述混合溶液冷却至室温，得到含有Cu(NCN)2的固体混合物。3) Slowly add 0.168g NaHCO 3 to the above mixed solution, the dark green solution turns black immediately, and precipitates out immediately, continue stirring until the reaction is complete. After the reaction, the mixed solution was cooled to room temperature to obtain a solid mixture containing Cu(NCN) 2 .
4)将该固体混合物分散至水中，通过离心收集黑色沉淀物，并用蒸馏水和乙醇洗涤三次，而后在60℃恒温、真空的条件下干燥12h，即可得到Cu(NCN)2。4) Disperse the solid mixture into water, collect the black precipitate by centrifugation, wash three times with distilled water and ethanol, and then dry at 60°C under constant temperature and vacuum for 12 hours to obtain Cu(NCN) 2 .
5)将所得Cu(NCN)2进行热处理，热处理工艺为：在N2气氛中以5℃/min的速率升温至350℃，保温2h之后随炉冷却至室温，取出后即可得Cu/Cu3N/C复合材料。5) Heat treatment of the obtained Cu(NCN) 2. The heat treatment process is as follows: in a N 2 atmosphere, the temperature is raised to 350° C. at a rate of 5° C./min. 3 N/C composites.
本实施例制备的Cu/Cu3N/C的扫描电子显微镜图片如图1所示，从图中可以看出，Cu/Cu3N/C的形貌为纳米颗粒团聚成的海胆状球形块体，尺寸为300～500nm。Cu/Cu3N/C的XRD射线衍射图如图2所示，可以看到其衍射峰的位置与标准卡片PDF 47-1088(Cu3N)、PDF04-0836(Cu)报道的结果一致，可判定本发明产物的物相为Cu/Cu3N/C。由此可见，本实施例制备得到的复合材料中氮化铜的物相为Cu3N，形貌为由粒径20～50nm小颗粒连接成300～500nm的海胆状大颗粒。The scanning electron microscope picture of the Cu/Cu 3 N/C prepared in this example is shown in Fig. 1. It can be seen from the figure that the morphology of the Cu/Cu 3 N/C is a sea urchin-shaped spherical block formed by agglomeration of nanoparticles body with a size of 300 to 500 nm. The XRD pattern of Cu/Cu 3 N/C is shown in Figure 2. It can be seen that the positions of its diffraction peaks are consistent with the results reported in standard cards PDF 47-1088 (Cu 3 N) and PDF04-0836 (Cu). It can be determined that the phase of the product of the present invention is Cu/Cu 3 N/C. It can be seen that the phase of copper nitride in the composite material prepared in this example is Cu 3 N, and the morphology is that small particles with a particle size of 20-50 nm are connected to large sea urchin-like particles with a particle size of 300-500 nm.
实施例2Example 2
1)在Ar保护性气氛下，将2.10g氨基氰加热至60℃，熔化完全至形成澄清透明溶液，在熔化过程中持续剧烈搅拌。1) Under Ar protective atmosphere, heat 2.10 g of cyanamide to 60°C, melt completely until a clear and transparent solution is formed, and continue to stir vigorously during the melting process.
2)将0.366g硝酸镍(Ni(NO3)2)加至上述熔融态氨基氰溶液中，继续保持搅拌至溶液变成灰褐色，得到混合溶液。2) 0.366g of nickel nitrate (Ni(NO 3 ) 2 ) was added to the above molten cyanamide solution, and the stirring was continued until the solution became gray-brown to obtain a mixed solution.
3)将0.420g NaHCO3缓慢加入上述混合溶液中，灰褐色的溶液立刻变成青绿色，并立即有沉淀析出，继续搅拌至反应完全。反应结束后，将上述混合溶液冷却至室温，得到含有Ni(HNCN)2的固体混合物。3) 0.420g NaHCO 3 was slowly added to the above mixed solution, the gray-brown solution immediately turned turquoise, and a precipitate appeared immediately, and continued stirring until the reaction was complete. After the reaction, the above mixed solution was cooled to room temperature to obtain a solid mixture containing Ni(HNCN) 2 .
4)将该固体混合物分散至水中，通过离心收集青绿色沉淀物，并用蒸馏水和乙醇洗涤三次，而后在60℃恒温、真空条件下干燥12h，即可得到Ni(HNCN)2。4) Disperse the solid mixture into water, collect the turquoise precipitate by centrifugation, wash three times with distilled water and ethanol, and then dry at 60°C under constant temperature and vacuum for 12 hours to obtain Ni(HNCN) 2 .
5)将所得Ni(HNCN)2进行热处理，热处理工艺为：在N2气氛中以2℃/min的速率升温至475℃，保温5h之后随炉冷却至室温，取出后即可得Ni/Ni3N/C复合材料。5) Heat treatment of the obtained Ni(HNCN) 2. The heat treatment process is as follows: in a N 2 atmosphere, the temperature is raised to 475° C. at a rate of 2° C./min. 3 N/C composites.
本实施例制备的Ni/Ni3N/C的XRD射线衍射图如图3所示，可以看到其衍射峰的位置与标准卡片PDF 10-0280(Ni3N)、PDF 04-0850(Ni)报道的结果一致，可判定本实施例得到的产物的物相为Ni/Ni3N/C。The XRD pattern of the Ni/Ni 3 N/C prepared in this example is shown in Fig. 3 . It can be seen that the positions of its diffraction peaks are the same as those of standard cards PDF 10-0280 (Ni 3 N) and PDF 04-0850 (Ni 3 N) ) are consistent with the reported results, and it can be determined that the phase of the product obtained in this example is Ni/Ni 3 N/C.
实施例3Example 3
1)在N2/Ar混合保护性气氛下，将4.20g氨基氰加热至80℃，熔化完全至形成澄清透明溶液，在熔化过程中持续剧烈搅拌。1) Under a mixed protective atmosphere of N 2 /Ar, 4.20 g of cyanamide was heated to 80° C., melted completely until a clear and transparent solution was formed, and vigorous stirring was continued during the melting process.
2)将0.177g乙酸钴(Co(CH3COO)2)加至上述熔融态氨基氰溶液中，继续保持搅拌至溶液变成浅蓝色，得到混合溶液。2) 0.177 g of cobalt acetate (Co(CH 3 COO) 2 ) was added to the molten cyanamide solution, and the stirring was continued until the solution turned light blue to obtain a mixed solution.
3)将0.420g NaHCO3缓慢加入上述混合溶液中，浅蓝色的溶液立刻变成粉紫色，并立即有沉淀析出，继续搅拌至反应完全。反应结束后，将上述混合溶液冷却至室温，得到含有Co(HNCN)2的固体混合物。3) 0.420g NaHCO 3 was slowly added to the above mixed solution, the light blue solution immediately turned pinkish purple, and a precipitate appeared immediately, and continued stirring until the reaction was complete. After the reaction, the mixed solution was cooled to room temperature to obtain a solid mixture containing Co(HNCN) 2 .
4)将该混合物分散至水中，通过离心收集粉紫色沉淀物，并用蒸馏水和乙醇洗涤三次，而后在60℃恒温、真空条件下干燥12h，即可得到Co(HNCN)2。4) Disperse the mixture into water, collect the pink-purple precipitate by centrifugation, wash three times with distilled water and ethanol, and then dry at 60°C under constant temperature and vacuum for 12 hours to obtain Co(HNCN) 2 .
5)将所得Co(HNCN)2进行热处理，热处理工艺为：在N2气氛中以2℃/min的速率升温至600℃，保温5h之后随炉冷却至室温，取出后即可得Co/Co3N/C复合材料。5) Heat treatment of the obtained Co(HNCN) 2 . The heat treatment process is as follows: in a N 2 atmosphere, the temperature is raised to 600° C. at a rate of 2° C./min. 3 N/C composites.
本实施例制备的氮化钴的物相为Co3N，其SEM照片如图4所示，从图中可以看出，其形貌为由300～400nm纳米颗粒团聚形成的更大的块体。The phase of the cobalt nitride prepared in this example is Co 3 N, and its SEM photo is shown in Figure 4. It can be seen from the figure that its morphology is a larger block formed by agglomeration of 300-400 nm nanoparticles .
实施例4Example 4
1)在Ar保护性气氛下，将0.420g氨基氰加热至70℃，熔化完全至形成澄清透明溶液，在熔化过程中持续剧烈搅拌。1) Under Ar protective atmosphere, heat 0.420 g of cyanamide to 70°C, melt completely until a clear and transparent solution is formed, and continue to stir vigorously during the melting process.
2)将0.152g硫酸亚铁(Fe(SO4))加至上述熔融态氨基氰溶液中，继续保持搅拌至溶液变成墨绿色，得到混合溶液。2) Add 0.152 g of ferrous sulfate (Fe(SO 4 )) to the molten cyanamide solution, and continue to keep stirring until the solution turns dark green to obtain a mixed solution.
3)将0.168g NaHCO3缓慢加入上述混合溶液中，墨绿色的溶液立刻变成淡绿色，并立即有沉淀析出，继续搅拌至反应完全。反应结束后，将上述混合溶液冷却至室温，得到含有Fe(HNCN)2的固体混合物。3) 0.168g NaHCO 3 was slowly added to the above mixed solution, the dark green solution immediately turned light green, and a precipitate appeared immediately, and continued stirring until the reaction was complete. After the reaction, the above mixed solution was cooled to room temperature to obtain a solid mixture containing Fe(HNCN) 2 .
4)将该固体混合物分散至水中，通过离心收集淡绿色沉淀物，并用蒸馏水和乙醇洗涤三次，而后在60℃恒温、真空条件下干燥12h，即可得到Fe(HNCN)2。4) Disperse the solid mixture into water, collect the pale green precipitate by centrifugation, wash three times with distilled water and ethanol, and then dry at a constant temperature of 60° C. and vacuum for 12 hours to obtain Fe(HNCN) 2 .
5)将所得Fe(HNCN)2进行热处理，热处理工艺为：在N2气氛中以10℃/min的速率升温至700℃，保温8h之后随炉冷却至室温，取出后即可得Fe/Fe3N/C复合材料。5) Heat treatment of the obtained Fe(HNCN) 2. The heat treatment process is as follows: in a N 2 atmosphere, the temperature is raised to 700° C. at a rate of 10° C./min. 3 N/C composites.
本实施例制备的氮化铁的物相为Fe3N，其XRD衍射图如图5所示，从图中可以看出，其衍射峰的位置与标准卡片PDF 49-1644(Fe3N)、PDF 06-0696(Fe)报道的结果一致，可判定产物的物相为Fe/Fe3N/C。The phase of iron nitride prepared in this example is Fe 3 N, and its XRD diffraction pattern is shown in Figure 5. It can be seen from the figure that the position of its diffraction peak is the same as that of the standard card PDF 49-1644 (Fe 3 N) , the results reported in PDF 06-0696 (Fe) are consistent, and it can be determined that the phase of the product is Fe/Fe 3 N/C.
实施例5Example 5
1)在N2保护性气氛下，将2.520g氨基氰加热至100℃，熔化完全至形成澄清透明溶液，在熔化过程中持续剧烈搅拌。1) Under a N2 protective atmosphere, heat 2.520 g of cyanamide to 100 °C, melt completely until a clear and transparent solution is formed, and continue to stir vigorously during the melting process.
2)将0.131g六水合硫酸镍和0.228硫酸亚铁(FeSO4)加至上述熔融态氨基氰溶液中，继续保持搅拌至溶液变成淡黄色，得到混合溶液。2) Add 0.131 g of nickel sulfate hexahydrate and 0.228 g of ferrous sulfate (FeSO 4 ) to the above molten cyanamide solution, and continue to keep stirring until the solution turns light yellow to obtain a mixed solution.
3)将0.420g NaHCO3缓慢加入上述混合溶液中，淡黄色的溶液立刻变成黑褐色，并立即有沉淀析出，继续搅拌至反应完全。反应结束后，将上述混合溶液冷却至室温，得到含有Ni0.25Fe0.75(HNCN)2的固体混合物。3) 0.420g NaHCO 3 was slowly added to the above mixed solution, the light yellow solution immediately turned black brown, and a precipitate appeared immediately, and continued stirring until the reaction was complete. After the reaction, the mixed solution was cooled to room temperature to obtain a solid mixture containing Ni 0.25 Fe 0.75 (HNCN) 2 .
4)将该固体混合物分散至水中，通过离心收集黑褐色沉淀物，并用蒸馏水和乙醇洗涤三次，而后在60℃恒温、真空条件下干燥12h，即可得到Ni0.25Fe0.75(HNCN)2。4) Disperse the solid mixture into water, collect the dark brown precipitate by centrifugation, wash with distilled water and ethanol three times, and then dry at 60°C under constant temperature and vacuum for 12 hours to obtain Ni 0.25 Fe 0.75 (HNCN) 2 .
5)将所得Ni0.25Fe0.75(HNCN)2进行热处理，热处理工艺为：在N2气氛中以20℃/min的速率升温至650℃，保温8h之后随炉冷却至室温，取出后即可得Fe/NiFe3N/C复合材料。5) The obtained Ni 0.25 Fe 0.75 (HNCN) 2 is subjected to heat treatment, and the heat treatment process is as follows: in a N 2 atmosphere, the temperature is increased to 650° C. at a rate of 20° C./min, and after being kept for 8 hours, it is cooled to room temperature with the furnace, and it can be obtained after taking out. Fe/NiFe 3 N/C composites.
通过表征可知，本实施例制备的过渡金属单质为Fe，而二元镍铁氮化物的物相为NiFe3N。It can be seen from the characterization that the transition metal element prepared in this example is Fe, and the phase of the binary nickel-iron nitride is NiFe 3 N.
通过上述实施例可知，在高温处理过程中，富碳、氮前驱体氢氰酸盐发生原位分解，一部分金属元素和氮元素结合转变为金属氮化物，而另一部分金属则碳热还原成单质，使得复合材料的成分包括过渡金属单质和过渡金属氮化物。本发明利用廉价的氨基氰、碳酸氢钠和金属前体(即金属盐)制备出相应的氢氰酸盐，而后通过对氢氰酸盐进一步的热处理即可得到相应的碳负载过渡金属/过渡金属氮化物复合材料。It can be seen from the above examples that in the process of high temperature treatment, the carbon- and nitrogen-rich precursor hydrogen cyanate is decomposed in situ, a part of metal elements and nitrogen elements are combined and transformed into metal nitrides, while another part of the metal is carbothermically reduced to elemental substances , so that the composition of the composite material includes transition metal element and transition metal nitride. The present invention utilizes cheap cyanamide, sodium bicarbonate and metal precursors (ie metal salts) to prepare the corresponding hydrogen cyanate, and then further heat treatment of the hydrogen cyanate can obtain the corresponding carbon-supported transition metal/transition metal Metal nitride composites.
以上所述的实施例只是本发明的一种较佳的方案，然其并非用以限制本发明。有关技术领域的普通技术人员，在不脱离本发明的精神和范围的情况下，还可以做出各种变化和变型。因此凡采取等同替换或等效变换的方式所获得的技术方案，均落在本发明的保护范围内。The above-mentioned embodiment is only a preferred solution of the present invention, but it is not intended to limit the present invention. Various changes and modifications can also be made by those of ordinary skill in the relevant technical field without departing from the spirit and scope of the present invention. Therefore, all technical solutions obtained by means of equivalent replacement or equivalent transformation fall within the protection scope of the present invention.
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