CN105858663B - A kind of preparation method of bowl-shape carbon and carbonization molybdenum composite material - Google Patents
A kind of preparation method of bowl-shape carbon and carbonization molybdenum composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000003763 carbonization Methods 0.000 title description 2
- 229910052750 molybdenum Inorganic materials 0.000 title description 2
- 239000011733 molybdenum Substances 0.000 title description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 29
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 22
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims abstract description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 5
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 5
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940079877 pyrogallol Drugs 0.000 claims abstract description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 239000002077 nanosphere Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- -1 molybdenum carbides Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
本发明涉及催化材料领域，具体是一种碗状碳与碳化钼复合材料的制备方法，其步骤为：将十六烷基三甲基溴化铵与二氧化硅微纳米球、对苯二酚或间苯二酚或邻苯三酚、甲醛溶液、水合肼以及钼酸铵或磷钼酸，混合搅拌、干燥，然后经煅烧和加热处理，获得复合材料。本发明所述一种碗状碳与碳化钼复合材料的制备方法，制备过程简单，操作方便，工艺参数易于控制，得到的碳颗粒具有碗状形貌，且粒度均匀，高度分散，与碳化钼符合得到的新型复合材料，有望用于催化领域。
The invention relates to the field of catalytic materials, in particular to a method for preparing a bowl-shaped carbon and molybdenum carbide composite material. or resorcinol or pyrogallol, formaldehyde solution, hydrazine hydrate, ammonium molybdate or phosphomolybdic acid, mixed and stirred, dried, and then calcined and heated to obtain a composite material. The preparation method of a bowl-shaped carbon and molybdenum carbide composite material of the present invention has simple preparation process, convenient operation, and easy control of process parameters. The obtained new composite material is expected to be used in the field of catalysis.
Description
技术领域technical field
本发明涉及催化材料领域，具体是一种碗状碳与碳化钼复合材料的制备方法。The invention relates to the field of catalytic materials, in particular to a method for preparing a bowl-shaped carbon and molybdenum carbide composite material.
背景技术Background technique
金属碳化物是一类具有高硬度、高熔点、良好热稳定性和抗腐蚀性的新型功能材料，已在许多领域得到应用。20 世纪 90 年代，Ledoux等报道金属碳化物具有类贵金属的特性，认为在金属碳化物中，碳原子间充在金属晶格中，引起电子密度的变化，使晶格参数变大，晶格间距增大，从而导致d带收缩，费米能态d电子密度增加，因而与贵金属有相似的表面性质和吸收特性。近年来，碳化物尤其是碳化钼作为一类新型催化材料引起广泛关注。就催化活性而言，碳化钼在许多方面与Pt族贵金属相似，特别是其析氢活性上与Pt、Pd等贵金属相当，有望成为贵金属的替代物。Metal carbides are a new class of functional materials with high hardness, high melting point, good thermal stability and corrosion resistance, and have been applied in many fields. In the 1990s, Ledoux et al. reported that metal carbides have the characteristics of noble metals. They believed that in metal carbides, carbon atoms are filled in the metal lattice, causing changes in electron density, increasing the lattice parameters, and the lattice spacing. Increase, resulting in shrinkage of the d-band, increase in the density of d electrons in the Fermi energy state, and thus have similar surface properties and absorption characteristics to noble metals. In recent years, carbides, especially molybdenum carbides, have attracted widespread attention as a new class of catalytic materials. In terms of catalytic activity, molybdenum carbide is similar to Pt noble metals in many aspects, especially its hydrogen evolution activity is comparable to noble metals such as Pt and Pd, and it is expected to become a substitute for noble metals.
随着研究的深入，新的制备碳化钼的方法也在不断提出和验证。目前，碳化钼的制备方法主要有以下几种 ：(1)程序升温反应法，将氧化钼前躯体在轻质烃或者轻质烃/H2混合气中程序升温碳化 (TPRe)。该方法简单易空及产物较纯，但该方法易导致催化剂表面积碳化，且所得碳化钼比表面积较小。(2)碳热还原法，由钼氧化物和适量的碳载体在保护气氛或者还原气氛中反应，该方法得到的产物具有较大的比表面积，但是该反应温度通常较高。(3)溶剂热还原法，该方法是采用还原能力强的物质 (KBH4)将氧化钼还原为碳化钼，该方法简单易控，温度较低，但是产物不纯，(4)金属前驱体裂解法，是利用金属有机化合物和利用钼酸铵与六次甲基四胺的混合物高温裂解制得，但是前驱体制备复杂，且制得颗粒较大。此外，还有CVD、水热法、超声法、微波法等报道，但是这些方法同样存在产量小，反应不充分、产物颗粒大、产物不纯的问题。以上的方法受限与本身特点而在实际应用特别是催化剂的量产方面存在较大的不足。With the deepening of research, new methods for preparing molybdenum carbide are constantly proposed and verified. At present, the preparation methods of molybdenum carbide mainly include the following: (1) temperature programmed reaction method, the precursor of molybdenum oxide is carbonized by temperature programming (TPRe) in light hydrocarbon or light hydrocarbon/H 2 mixed gas. The method is simple and easy to empty and the product is relatively pure, but the method easily leads to carbonization of the surface area of the catalyst, and the specific surface area of the obtained molybdenum carbide is small. (2) Carbothermal reduction method, which reacts molybdenum oxide and an appropriate amount of carbon carrier in a protective atmosphere or a reducing atmosphere. The product obtained by this method has a larger specific surface area, but the reaction temperature is usually higher. (3) Solvothermal reduction method, which is to reduce molybdenum oxide to molybdenum carbide by using a substance with strong reducing ability (KBH4). This method is simple and easy to control, and the temperature is low, but the product is impure. (4) Metal precursor cracking The method is to use metal organic compounds and high temperature pyrolysis of the mixture of ammonium molybdate and hexamethylenetetramine, but the preparation of the precursor is complicated and the obtained particles are relatively large. In addition, there are reports of CVD, hydrothermal method, ultrasonic method, microwave method, etc., but these methods also have the problems of small yield, insufficient reaction, large product particles, and impure products. The above methods are limited and have their own characteristics, so there are big deficiencies in practical application, especially in the mass production of catalysts.
发明内容Contents of the invention
本发明旨在提供一种新型复合催化材料，具体是一种碗状碳与碳化钼复合材料的制备方法。The invention aims to provide a novel composite catalytic material, specifically a method for preparing a bowl-shaped carbon and molybdenum carbide composite material.
本发明是通过以下技术方案实现的：一种碗状碳与碳化钼复合材料的制备方法，其是通过以下步骤实现的：The present invention is achieved through the following technical solutions: a preparation method of bowl-shaped carbon and molybdenum carbide composite material, which is achieved through the following steps:
（1）将十六烷基三甲基溴化铵充分溶解于体积比为1:2的乙醇和水的混合液中形成0.6～4g/L的十六烷基三甲基溴化铵溶液，加入与十六烷基三甲基溴化铵摩尔比为0.1～0.6：5～6的二氧化硅微纳米球，分散均匀后，加入与十六烷基三甲基溴化铵摩尔比为0.1～0.6：0.9～2的对苯二酚或间苯二酚或邻苯三酚，然后加入甲醛溶液，所述甲醛溶液中甲醛与十六烷基三甲基溴化铵摩尔比为0.1～0.6：5～10；再加入与十六烷基三甲基溴化铵摩尔比为0.1～0.6：7～14的水合肼，最后加入与十六烷基三甲基溴化铵摩尔比为0.1～0.6：1～6的钼酸铵或磷钼酸，室温搅拌15-18h后，干燥得到固体粉末；(1) Fully dissolve cetyltrimethylammonium bromide in a mixture of ethanol and water with a volume ratio of 1:2 to form a 0.6-4g/L cetyltrimethylammonium bromide solution, Add silicon dioxide micronanospheres with a molar ratio of 0.1 to 0.6:5 to 6 to cetyltrimethylammonium bromide, and after uniform dispersion, add a molar ratio of 0.1 to cetyltrimethylammonium bromide ～0.6: 0.9～2 hydroquinone or resorcinol or pyrogallol, and then add formaldehyde solution, the molar ratio of formaldehyde and cetyltrimethylammonium bromide in the formaldehyde solution is 0.1～0.6 : 5~10; then add hydrazine hydrate with cetyltrimethylammonium bromide molar ratio of 0.1~0.6:7~14, and finally add cetyltrimethylammonium bromide molar ratio of 0.1~ 0.6: 1-6 ammonium molybdate or phosphomolybdic acid, after stirring at room temperature for 15-18 hours, dry to obtain solid powder;
（2）、将步骤（1）中得到的固体粉末在700～900oC下煅烧3小时，得到复合材料初品；(2) Calcining the solid powder obtained in step (1) at 700-900 o C for 3 hours to obtain the primary product of the composite material;
（3）、将步骤（2）中得到的初级产品，加入到2mol/L氢氧化钠溶液中，在100～120oC下加热处理18小时，即得到碗状碳与碳化钼复合材料。(3) Add the primary product obtained in step (2) to 2mol/L sodium hydroxide solution, and heat it at 100-120 o C for 18 hours to obtain a bowl-shaped carbon and molybdenum carbide composite material.
本发明中十六烷基三甲基溴化铵的作用在于分散和修饰二氧化硅微纳米球；二氧化硅微纳米球的作用在于充当模板剂，使其表面包覆有机反应产物；对苯二酚（间苯二酚或间苯三酚）和甲醛的作用在于充当反应物，提供碳的前驱体；水合肼的作用在于提供反应需要的碱性环境。其中十六烷基三甲基溴化铵、二氧化硅微纳米球和后处理（加热处理）使得碳颗粒形成碗状碳形貌。In the present invention, the function of cetyltrimethylammonium bromide is to disperse and modify silica micro-nanospheres; the function of silica micro-nanospheres is to act as a template to coat the surface with organic reaction products; The role of diphenol (resorcinol or phloroglucinol) and formaldehyde is to act as a reactant and provide a carbon precursor; the role of hydrazine hydrate is to provide the alkaline environment required for the reaction. Among them, hexadecyltrimethylammonium bromide, silica micro-nanospheres and post-treatment (heat treatment) make the carbon particles form a bowl-shaped carbon morphology.
本发明所述一种碗状碳与碳化钼复合材料的制备方法，制备过程简单，操作方便，工艺参数易于控制，得到的碳颗粒具有碗状形貌，且粒度均匀，高度分散，与碳化钼符合得到的新型复合材料，有望用于催化领域。The preparation method of a bowl-shaped carbon and molybdenum carbide composite material of the present invention has simple preparation process, convenient operation, and easy control of process parameters. The obtained new composite material is expected to be used in the field of catalysis.
附图说明Description of drawings
图1为通过本发明所述方法制备获得的碗状碳与碳化钼复合材料的扫描电镜图。Fig. 1 is a scanning electron microscope image of a bowl-shaped carbon and molybdenum carbide composite material prepared by the method of the present invention.
图2为复合材料的透射电镜图。Figure 2 is a transmission electron microscope image of the composite material.
图3为通过本发明所述方法制备获得的碗状碳与碳化钼复合材料的XRD图。Fig. 3 is the XRD pattern of the bowl-shaped carbon and molybdenum carbide composite material prepared by the method of the present invention.
具体实施方式detailed description
实施例1Example 1
一种碗状碳与碳化钼复合材料的制备方法，其是通过以下步骤实现的：A kind of preparation method of bowl-shaped carbon and molybdenum carbide composite material, it is realized by following steps:
（1）将十六烷基三甲基溴化铵充分溶解于体积比为1:2的乙醇和水的混合液中形成0.6g/L的十六烷基三甲基溴化铵溶液，加入与十六烷基三甲基溴化铵摩尔比为0.3：6的二氧化硅微纳米球，分散均匀后，加入与十六烷基三甲基溴化铵摩尔比为0.1：1.5的对苯二酚，然后加入甲醛溶液，所述十六烷基三甲基溴化铵与甲醛溶液中甲醛摩尔比为0.6：5；再加入与十六烷基三甲基溴化铵摩尔比为0.3：14的水合肼，最后加入与十六烷基三甲基溴化铵摩尔比为0.1：3的钼酸铵，室温搅拌18h后，干燥得到固体粉末；(1) Fully dissolve cetyltrimethylammonium bromide in a mixture of ethanol and water with a volume ratio of 1:2 to form a 0.6g/L cetyltrimethylammonium bromide solution, add Silica micro-nanospheres with a molar ratio of 0.3:6 to cetyltrimethylammonium bromide, after uniform dispersion, add p-benzene with a molar ratio of 0.1:1.5 to cetyltrimethylammonium bromide Diphenol, then add formaldehyde solution, the molar ratio of formaldehyde in the described cetyltrimethylammonium bromide and formaldehyde solution is 0.6:5; Then add and cetyltrimethylammonium bromide molar ratio is 0.3: 14 hydrazine hydrate, finally add ammonium molybdate with a molar ratio of 0.1:3 to cetyltrimethylammonium bromide, stir at room temperature for 18 hours, and dry to obtain a solid powder;
（2）、将步骤（1）中得到的固体粉末在700oC下煅烧3小时，得到复合材料初品；(2) Calcining the solid powder obtained in step (1) at 700 o C for 3 hours to obtain the primary product of the composite material;
（3）、将步骤（2）中得到的初级产品，加入到2mol/L氢氧化钠溶液中，在110oC下加热处理18小时，即得到碗状碳与碳化钼复合材料。(3) The primary product obtained in step (2) was added to 2mol/L sodium hydroxide solution, and heated at 110 o C for 18 hours to obtain a bowl-shaped carbon and molybdenum carbide composite material.
实施例2Example 2
一种碗状碳与碳化钼复合材料的制备方法，其是通过以下步骤实现的：A kind of preparation method of bowl-shaped carbon and molybdenum carbide composite material, it is realized by following steps:
（1）将十六烷基三甲基溴化铵充分溶解于体积比为1:2的乙醇和水的混合液中形成2g/L的十六烷基三甲基溴化铵溶液，加入与十六烷基三甲基溴化铵摩尔比为0.6：5的二氧化硅微纳米球，分散均匀后，加入与十六烷基三甲基溴化铵摩尔比为0.3：2的间苯二酚，然后加入甲醛溶液，所述甲醛溶液中甲醛与十六烷基三甲基溴化铵摩尔比为0.1：8；再加入与十六烷基三甲基溴化铵摩尔比为0.6：7的水合肼，最后加入与十六烷基三甲基溴化铵摩尔比为0.3： 6的磷钼酸，室温搅拌15h后，干燥得到固体粉末；(1) Fully dissolve cetyltrimethylammonium bromide in a mixture of ethanol and water with a volume ratio of 1:2 to form a 2g/L cetyltrimethylammonium bromide solution, add Silica micro-nanospheres with cetyltrimethylammonium bromide molar ratio of 0.6:5, after uniform dispersion, add isophthalic diphenylbenzene with cetyltrimethylammonium bromide molar ratio Phenol, then add formaldehyde solution, the molar ratio of formaldehyde and cetyltrimethylammonium bromide in the said formaldehyde solution is 0.1:8; hydrazine hydrate, and finally add phosphomolybdic acid with cetyltrimethylammonium bromide molar ratio of 0.3: 6, after stirring at room temperature for 15h, dry to obtain solid powder;
（2）、将步骤（1）中得到的固体粉末在800oC下煅烧3小时，得到复合材料初品；(2) Calcining the solid powder obtained in step (1) at 800 o C for 3 hours to obtain the primary product of the composite material;
（3）、将步骤（2）中得到的初级产品，加入到2mol/L氢氧化钠溶液中，在120oC下加热处理18小时，即得到碗状碳与碳化钼复合材料。(3) The primary product obtained in step (2) was added to 2mol/L sodium hydroxide solution, and heated at 120 o C for 18 hours to obtain a bowl-shaped carbon and molybdenum carbide composite material.
实施例3Example 3
一种碗状碳与碳化钼复合材料的制备方法，其是通过以下步骤实现的：A kind of preparation method of bowl-shaped carbon and molybdenum carbide composite material, it is realized by following steps:
（1）将十六烷基三甲基溴化铵充分溶解于体积比为1:2的乙醇和水的混合液中形成4g/L的十六烷基三甲基溴化铵溶液，加入与十六烷基三甲基溴化铵摩尔比为0.1：5.5的二氧化硅微纳米球，分散均匀后，加入与十六烷基三甲基溴化铵摩尔比为0.6：0.9的邻苯三酚，然后加入甲醛溶液，所述甲醛溶液中甲醛与十六烷基三甲基溴化铵摩尔比为0.3：10；再加入与十六烷基三甲基溴化铵摩尔比为0.1：10的水合肼，最后加入与十六烷基三甲基溴化铵摩尔比为0.6：1磷钼酸，室温搅拌17h后，干燥得到固体粉末；(1) Fully dissolve cetyltrimethylammonium bromide in a mixture of ethanol and water with a volume ratio of 1:2 to form a 4g/L cetyltrimethylammonium bromide solution, add Silica micro-nanospheres with cetyltrimethylammonium bromide molar ratio of 0.1:5.5, after uniform dispersion, add phthalic trimethylammonium bromide with cetyltrimethylammonium bromide molar ratio of 0.6:0.9 Phenol, then add formaldehyde solution, the molar ratio of formaldehyde and cetyltrimethylammonium bromide in the said formaldehyde solution is 0.3:10; hydrazine hydrate, finally added phosphomolybdic acid in a molar ratio of 0.6:1 to cetyltrimethylammonium bromide, stirred at room temperature for 17 hours, and dried to obtain a solid powder;
（2）、将步骤（1）中得到的固体粉末在900oC下煅烧3小时，得到复合材料初品；(2) Calcining the solid powder obtained in step (1) at 900 o C for 3 hours to obtain the primary product of the composite material;
（3）、将步骤（2）中得到的初级产品，加入到2mol/L氢氧化钠溶液中，在100oC下加热处理18小时，即得到碗状碳与碳化钼复合材料。(3) The primary product obtained in step (2) was added to 2mol/L sodium hydroxide solution, and heated at 100 o C for 18 hours to obtain a bowl-shaped carbon and molybdenum carbide composite material.
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