CN113716608B - A kind of molybdenum dioxide-molybdenum carbide composite material and its preparation method and application - Google Patents
A kind of molybdenum dioxide-molybdenum carbide composite material and its preparation method and application Download PDFInfo
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- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 151
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- UNSSZNICXIOSLT-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O.[Mo]=O UNSSZNICXIOSLT-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims abstract description 68
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- 229910003178 Mo2C Inorganic materials 0.000 description 7
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- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- ZGHDMISTQPRNRG-UHFFFAOYSA-N dimolybdenum Chemical compound [Mo]#[Mo] ZGHDMISTQPRNRG-UHFFFAOYSA-N 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract
Description
技术领域technical field
本发明涉及异质结构材料技术领域，具体涉及一种二氧化钼-碳化钼复合材料及其制备方法和应用。The invention relates to the technical field of heterostructured materials, in particular to a molybdenum dioxide-molybdenum carbide composite material and a preparation method and application thereof.
背景技术Background technique
电催化析氢是一种电解水制备氢气的方法，具有清洁无污染的优点，但由于电解水反应存在较高的反应能量壁垒，成本较高。因此，开发高效、低成本的电解水催化剂对于制氢产业而言具有十分重要的意义。Electrocatalytic hydrogen evolution is a method for preparing hydrogen by electrolysis of water, which has the advantages of clean and pollution-free, but due to the high reaction energy barrier of the water electrolysis reaction, the cost is high. Therefore, the development of efficient and low-cost catalysts for water electrolysis is of great significance for the hydrogen production industry.
钼基材料(例如：碳化钼、二氧化钼、二硫化钼等)用作电解水催化剂具有不错的催化效果，近些年来受到了研究人员的广泛关注。然而，现有的钼基材料普遍存在制备工艺复杂、产率低、能耗高、制备过程会污染环境等问题，难以真正实现大规模工业应用，例如：CN109499592 A公开了一种纳米棒碳化钼/二氧化钼复合材料，是通过将钼酸铵溶液和单宁酸溶液混合后在800℃～900℃下进行高温热处理得到，该纳米棒碳化钼/二氧化钼复合材料可以用于催化领域，但其在制备过程中需要进行高温热处理，能耗高，且还会产生废液，后续需要进行无害化处理；Gao等人通过采用氧等离子体处理Mo2C，在其表面原位生成MoOx，得到了具有Mo2C/MoOx异质结构的复合材料，其在电催化水解的测试中表现出优异的催化性能，但由于该复合材料的制备工艺复杂，产率较低，难以实现工业应用(Angew.Chem.Int.Ed.2020,59,3544-3548)。Molybdenum-based materials (such as molybdenum carbide, molybdenum dioxide, molybdenum disulfide, etc.) have good catalytic effects as catalysts for water electrolysis, and have received extensive attention from researchers in recent years. However, the existing molybdenum-based materials generally have problems such as complex preparation process, low yield, high energy consumption, and environmental pollution during the preparation process, and it is difficult to achieve large-scale industrial applications. For example: CN109499592 A discloses a nanorod molybdenum carbide The nanorod molybdenum carbide/molybdenum dioxide composite material is obtained by mixing ammonium molybdate solution and tannic acid solution and then performing high temperature heat treatment at 800℃～900℃. The nanorod molybdenum carbide/molybdenum dioxide composite material can be used in the field of catalysis. However, it requires high temperature heat treatment in the preparation process, high energy consumption, and also generates waste liquid, which requires subsequent harmless treatment; Gao et al. used oxygen plasma to treat Mo 2 C to generate MoO in situ on its surface x , a composite material with Mo 2 C/MoO x heterostructure was obtained, which showed excellent catalytic performance in the test of electrocatalytic hydrolysis, but due to the complex preparation process and low yield of the composite material, it was difficult to achieve Industrial applications (Angew. Chem. Int. Ed. 2020, 59, 3544-3548).
因此，亟需开发一种催化活性好、制备简单、能耗低、成本低的电解水催化剂。Therefore, there is an urgent need to develop a water electrolysis catalyst with good catalytic activity, simple preparation, low energy consumption and low cost.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种二氧化钼-碳化钼复合材料及其制备方法和应用。The purpose of the present invention is to provide a molybdenum dioxide-molybdenum carbide composite material and its preparation method and application.
本发明所采取的技术方案是：The technical scheme adopted by the present invention is:
一种二氧化钼-碳化钼复合材料，其组成包括MoO2和MoC，还可以包括Mo2C。A molybdenum dioxide-molybdenum carbide composite material is composed of MoO 2 and MoC, and can also include Mo 2 C.
上述二氧化钼-碳化钼复合材料的制备方法包括以下步骤：将二氧化钼、镁粉和碳氮化物混合，进行固相球磨、酸洗和干燥，即得二氧化钼-碳化钼复合材料。The preparation method of the molybdenum dioxide-molybdenum carbide composite material includes the following steps: mixing molybdenum dioxide, magnesium powder and carbonitride, performing solid-phase ball milling, pickling and drying to obtain the molybdenum dioxide-molybdenum carbide composite material.
优选的，所述二氧化钼、镁粉、碳氮化物的摩尔比为1:6～9:0.3～2。Preferably, the molar ratio of the molybdenum dioxide, magnesium powder and carbonitride is 1:6-9:0.3-2.
优选的，所述碳氮化物为三聚氰胺、氮化碳中的至少一种。Preferably, the carbonitride is at least one of melamine and carbon nitride.
优选的，所述固相球磨在保护气氛中进行。Preferably, the solid phase ball milling is carried out in a protective atmosphere.
优选的，所述保护气氛为氩气气氛。Preferably, the protective atmosphere is an argon atmosphere.
优选的，所述固相球磨在室温(15℃～35℃)下进行。Preferably, the solid-phase ball milling is performed at room temperature (15°C to 35°C).
优选的，所述固相球磨采用的球磨机为高速摆振式球磨机，球料比为10:1～100:1，球磨机转速为1000rpm～1230rpm，球磨时间为2h～6h。Preferably, the ball mill used in the solid phase ball milling is a high-speed pendulum ball mill, the ball-to-material ratio is 10:1-100:1, the ball mill rotational speed is 1000rpm-1230rpm, and the ball-milling time is 2h-6h.
优选的，所述固相球磨采用的球磨机为行星式球磨机，球料比为20:1～100:1，球磨机转速为400rpm～500rpm，球磨时间为8h～20h。Preferably, the ball mill used in the solid phase ball milling is a planetary ball mill, the ball-to-material ratio is 20:1-100:1, the ball mill rotational speed is 400rpm-500rpm, and the ball-milling time is 8h-20h.
优选的，所述固相球磨间歇式进行，每球磨30min暂停30min。Preferably, the solid-phase ball milling is performed intermittently, and the ball milling is suspended for 30 minutes every 30 minutes.
优选的，所述酸洗采用的酸为盐酸、硫酸、磷酸中的一种。Preferably, the acid used in the pickling is one of hydrochloric acid, sulfuric acid and phosphoric acid.
优选的，所述盐酸的浓度为1mol/L～6mol/L。Preferably, the concentration of the hydrochloric acid is 1 mol/L to 6 mol/L.
优选的，所述硫酸的浓度为1mol/L～6mol/L。Preferably, the concentration of the sulfuric acid is 1 mol/L to 6 mol/L.
优选的，所述磷酸的质量分数为15％～25％。Preferably, the mass fraction of the phosphoric acid is 15% to 25%.
本发明的有益效果是：本发明的二氧化钼-碳化钼复合材料的组成包括MoO2和MoC，还可以包括Mo2C，将其用作电催化析氢反应的催化剂具有很好的催化活性，且其制备方法简单、能耗低、成本低，适合大规模生产应用。The beneficial effects of the present invention are: the composition of the molybdenum dioxide-molybdenum carbide composite material of the present invention includes MoO 2 and MoC, and can also include Mo 2 C, and it has good catalytic activity when used as a catalyst for electrocatalytic hydrogen evolution reaction, And the preparation method is simple, low in energy consumption and low in cost, and is suitable for large-scale production and application.
具体来说：Specifically:
1)本发明通过固相球磨的方式在二氧化钼表面进行原位还原与渗碳，得到原位生长的二氧化钼-碳化钼异质结构材料，且通过镁粉来调控MoC相和Mo2C相的比例；1) The present invention performs in-situ reduction and carburizing on the surface of molybdenum dioxide by means of solid-phase ball milling to obtain an in-situ growth molybdenum dioxide-molybdenum carbide heterostructure material, and the MoC phase and Mo 2 are regulated by magnesium powder. The proportion of phase C;
2)本发明的二氧化钼-碳化钼复合材料在酸性和碱性条件下均展现出优异的催化活性，具有很好的应用前景；2) The molybdenum dioxide-molybdenum carbide composite material of the present invention exhibits excellent catalytic activity under both acidic and basic conditions, and has good application prospects;
3)本发明的二氧化钼-碳化钼复合材料的制备过程简单，生产周期短，可控性强，无需进行高温热处理，且全程无需引入额外热源，能耗低，成本低，污染极小。3) The preparation process of the molybdenum dioxide-molybdenum carbide composite material of the present invention is simple, the production cycle is short, the controllability is strong, no high temperature heat treatment is required, and no additional heat source is introduced in the whole process, the energy consumption is low, the cost is low, and the pollution is extremely small.
附图说明Description of drawings
图1为实施例1、4和7的二氧化钼-碳化钼复合材料XRD图。FIG. 1 is the XRD patterns of the molybdenum dioxide-molybdenum carbide composites of Examples 1, 4 and 7. FIG.
图2为实施例1、4、7、10和13的二氧化钼-碳化钼复合材料在碱性条件下的电化学析氢LSV曲线。2 is the electrochemical hydrogen evolution LSV curves of the molybdenum dioxide-molybdenum carbide composites of Examples 1, 4, 7, 10 and 13 under alkaline conditions.
图3为实施例1、4、7、10和13的二氧化钼-碳化钼复合材料在酸性条件下的电化学析氢LSV曲线。3 is the electrochemical hydrogen evolution LSV curves of the molybdenum dioxide-molybdenum carbide composites of Examples 1, 4, 7, 10 and 13 under acidic conditions.
图4为实施例4的二氧化钼-碳化钼复合材料的SEM图。FIG. 4 is a SEM image of the molybdenum dioxide-molybdenum carbide composite material of Example 4. FIG.
图5为实施例10和13的二氧化钼-碳化钼复合材料XRD图。5 is an XRD pattern of the molybdenum dioxide-molybdenum carbide composites of Examples 10 and 13.
图6为实施例16和17的二氧化钼-碳化钼复合材料XRD图。6 is an XRD pattern of the molybdenum dioxide-molybdenum carbide composites of Examples 16 and 17. FIG.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步的解释和说明。The present invention will be further explained and illustrated below in conjunction with specific embodiments.
实施例1：Example 1:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:6:0.3混合装入球磨罐，并按照球料比50:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1230转/分钟，氩气气氛中球磨2h，再将球磨产物加入浓度1mol/L的盐酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1 MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:6:0.3 and put them into the ball mill tank, and according to the ball-to-material ratio of 50 : 1 Add the ball milling medium, then add the ball milling tank to the high-energy pendulum ball mill, adjust the ball mill speed to 1230 rpm, ball mill in an argon atmosphere for 2 hours, and then add the ball mill product to a concentration of 1mol/L hydrochloric acid solution, stir, centrifuge , wash the solid obtained by centrifugation until neutral, and then place it in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
性能测试：Performance Testing:
1)本实施例的二氧化钼-碳化钼复合材料的X射线衍射(XRD)图如图1所示。1) The X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of this embodiment is shown in FIG. 1 .
由图1可知：可以观察到MoC、Mo2C和MoO2的特征峰，即本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成。It can be seen from Fig. 1 that characteristic peaks of MoC, Mo 2 C and MoO 2 can be observed, that is, the molybdenum dioxide-molybdenum carbide composite material of this embodiment is composed of MoC, Mo 2 C and MoO 2 .
2)本实施例的二氧化钼-碳化钼复合材料在碱性条件(1mol/L的KOH溶液)和酸性条件(0.5mol/L的H2SO4溶液)下的电化学析氢LSV曲线(测试在三电极体系中完成，对电极为石墨电极，参比电极为银/氯化银电极，扫描速度为5mV/s)依次如图2和图3所示。2) The electrochemical hydrogen evolution LSV curve of the molybdenum dioxide-molybdenum carbide composite material of this embodiment under alkaline conditions (1 mol/L KOH solution) and acidic conditions (0.5 mol/L H 2 SO 4 solution) (test Completed in a three-electrode system, the counter electrode is a graphite electrode, the reference electrode is a silver/silver chloride electrode, and the scanning speed is 5mV/s) as shown in Figure 2 and Figure 3 in turn.
由图2和图3可知：本实施例的二氧化钼-碳化钼复合材料在碱性条件和酸性条件下均展现出优异的催化性能。It can be seen from FIG. 2 and FIG. 3 that the molybdenum dioxide-molybdenum carbide composite material of this embodiment exhibits excellent catalytic performance under both alkaline conditions and acidic conditions.
实施例2：Example 2:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:8:0.3混合装入球磨罐，并按照球料比50:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1100转/分钟，氩气气氛中球磨2h，再将球磨产物加入浓度1mol/L的硫酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:8:0.3 and put them into the ball mill tank, and according to the ball-to-material ratio of 50 : 1 Add the ball milling medium, then add the ball milling tank to the high-energy pendulum ball mill, adjust the ball mill speed to 1100 rpm, ball mill in an argon atmosphere for 2 hours, and then add the ball mill product to a concentration of 1mol/L sulfuric acid solution, stir, centrifuge , wash the solid obtained by centrifugation until neutral, and then place it in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成，其催化性能与实施例1的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide-molybdenum carbide composite material of this example is composed of MoC, Mo 2 C and MoO 2 , and its catalytic performance is very close to that of the molybdenum dioxide-molybdenum carbide composite material of Example 1.
实施例3：Example 3:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:9:0.3混合装入球磨罐，并按照球料比10:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1000转/分钟，氩气气氛中球磨2h，再将球磨产物加入质量分数25％的磷酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1 MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:9:0.3 and put them into the ball mill tank, and according to the ball-to-material ratio of 10 : 1 Add the ball milling medium, then add the ball milling tank to the high-energy pendulum ball mill, adjust the ball mill speed to 1000 rpm, ball mill in an argon atmosphere for 2 hours, and then add the ball mill product to a mass fraction of 25% phosphoric acid solution, stir, centrifuge , wash the solid obtained by centrifugation until neutral, and then place it in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成，其催化性能与实施例1的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide-molybdenum carbide composite material of this example is composed of MoC, Mo 2 C and MoO 2 , and its catalytic performance is very close to that of the molybdenum dioxide-molybdenum carbide composite material of Example 1.
实施例4：Example 4:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:6:1混合装入球磨罐，并按照球料比50:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1230转/分钟，氩气气氛中球磨6h，再将球磨产物加入浓度3mol/L的盐酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:6:1 and put them into the ball mill tank, and according to the ball-to-material ratio of 50 : 1 Add the ball milling medium, then add the ball milling tank to the high-energy pendulum ball mill, adjust the ball mill speed to 1230 rpm, ball mill in an argon atmosphere for 6 hours, and then add the ball mill product to a concentration of 3mol/L hydrochloric acid solution, stir, centrifuge , wash the solid obtained by centrifugation until neutral, and then place it in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
性能测试：Performance Testing:
1)本实施例的二氧化钼-碳化钼复合材料的X射线衍射(XRD)图如图1所示。1) The X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of this embodiment is shown in FIG. 1 .
由图1可知：可以观察到MoC、Mo2C和MoO2的特征峰，其中MoC为主相，即本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成。It can be seen from Figure 1 that characteristic peaks of MoC, Mo2C and MoO2 can be observed, wherein MoC is the main phase, that is, the molybdenum dioxide - molybdenum carbide composite material of this embodiment is composed of MoC, Mo2C and MoO2 .
2)本实施例的二氧化钼-碳化钼复合材料的扫描电镜(SEM)图如图4所示。2) The scanning electron microscope (SEM) image of the molybdenum dioxide-molybdenum carbide composite material of this embodiment is shown in FIG. 4 .
由图4可知：酸洗后的终产物无特殊形貌，大颗粒材料由纳米颗粒表面团聚而成，体相内部存在孔道结构。It can be seen from Figure 4 that the final product after pickling has no special morphology, the large particle material is formed by agglomeration on the surface of the nanoparticles, and there is a pore structure in the bulk phase.
3)本实施例的二氧化钼-碳化钼复合材料在碱性条件(1mol/L的KOH溶液)和酸性条件(0.5mol/L的H2SO4溶液)下的电化学析氢LSV曲线(测试方法同实施例1)依次如图2和图3所示。3) The electrochemical hydrogen evolution LSV curve (test) of the molybdenum dioxide-molybdenum carbide composite material of this embodiment under alkaline conditions (1 mol/L KOH solution) and acidic conditions (0.5 mol/L H 2 SO 4 solution). The method is the same as in Example 1) shown in Figure 2 and Figure 3 in turn.
由图2和图3可知：本实施例的二氧化钼-碳化钼复合材料在碱性条件和酸性条件下均展现出优异的催化性能。It can be seen from FIG. 2 and FIG. 3 that the molybdenum dioxide-molybdenum carbide composite material of this embodiment exhibits excellent catalytic performance under both alkaline conditions and acidic conditions.
实施例5：Example 5:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:8:1混合装入球磨罐，并按照球料比50:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1100转/分钟，氩气气氛中球磨2h，再将球磨产物加入浓度3mol/L的硫酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:8:1 and put them into the ball mill tank, and according to the ball-to-material ratio of 50 : 1 Add the ball milling medium, then add the ball milling jar to the high-energy pendulum ball mill, adjust the ball mill speed to 1100 rpm, ball mill in an argon atmosphere for 2 hours, and then add the ball mill product to a concentration of 3mol/L sulfuric acid solution, stir, centrifuge , wash the solid obtained by centrifugation until neutral, and then place it in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成，其催化性能与实施例4的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide-molybdenum carbide composite material of this example is composed of MoC, Mo 2 C and MoO 2 , and its catalytic performance is very close to that of the molybdenum dioxide-molybdenum carbide composite material of Example 4.
实施例6：Example 6:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:9:1混合装入球磨罐，并按照球料比10:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1000转/分钟，氩气气氛中球磨2h，再将球磨产物加入质量分数20％的磷酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:9:1 and put them into the ball mill tank, and according to the ball-to-material ratio of 10 : 1 Add the ball milling medium, then add the ball mill tank to the high-energy pendulum ball mill, adjust the ball mill speed to 1000 rpm, ball mill in an argon atmosphere for 2 hours, and then add the ball mill product to a mass fraction of 20% phosphoric acid solution, stir, centrifuge , wash the solid obtained by centrifugation until neutral, and then place it in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成，其催化性能与实施例4的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide-molybdenum carbide composite material of this example is composed of MoC, Mo 2 C and MoO 2 , and its catalytic performance is very close to that of the molybdenum dioxide-molybdenum carbide composite material of Example 4.
实施例7：Example 7:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:6:2混合装入球磨罐，并按照球料比50:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1230转/分钟，氩气气氛中球磨6h，再将球磨产物加入浓度6mol/L的盐酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:6:2 and put them into the ball mill tank, and according to the ball-to-material ratio of 50 : 1 Add the ball milling medium, then add the ball milling tank to the high-energy pendulum ball mill, adjust the ball mill speed to 1230 rpm, ball mill in an argon atmosphere for 6 hours, and then add the ball mill product to a concentration of 6mol/L hydrochloric acid solution, stir, centrifuge , wash the solid obtained by centrifugation until neutral, and then place it in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
性能测试：Performance Testing:
1)本实施例的二氧化钼-碳化钼复合材料的X射线衍射(XRD)图如图1所示。1) The X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of this embodiment is shown in FIG. 1 .
由图1可知：可以观察到MoC和MoO2的特征峰，即本实施例的二氧化钼-碳化钼复合材料由MoC和MoO2组成。It can be seen from Figure 1 that the characteristic peaks of MoC and MoO 2 can be observed, that is, the molybdenum dioxide-molybdenum carbide composite material of this embodiment is composed of MoC and MoO 2 .
2)本实施例的二氧化钼-碳化钼复合材料在碱性条件(1mol/L的KOH溶液)和酸性条件(0.5mol/L的H2SO4溶液)下的电化学析氢LSV曲线(测试方法同实施例1)依次如图2和图3所示。2) The electrochemical hydrogen evolution LSV curve of the molybdenum dioxide-molybdenum carbide composite material of this embodiment under alkaline conditions (1 mol/L KOH solution) and acidic conditions (0.5 mol/L H 2 SO 4 solution) (test The method is the same as in Example 1) shown in Figure 2 and Figure 3 in turn.
由图2和图3可知：本实施例的二氧化钼-碳化钼复合材料在碱性条件和酸性条件下均展现出优异的催化性能。It can be seen from FIG. 2 and FIG. 3 that the molybdenum dioxide-molybdenum carbide composite material of this embodiment exhibits excellent catalytic performance under both alkaline conditions and acidic conditions.
实施例8：Example 8:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:8:2混合装入球磨罐，并按照球料比50:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1100转/分钟，氩气气氛中球磨6h，再将球磨产物加入浓度6mol/L的硫酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:8:2 and put them into the ball mill tank, and according to the ball-to-material ratio of 50 : 1 Add the ball milling medium, then add the ball milling jar to the high-energy pendulum ball mill, adjust the ball mill speed to 1100 rpm, ball mill in an argon atmosphere for 6 hours, and then add the ball mill product to a concentration of 6mol/L sulfuric acid solution, stir, centrifuge , wash the solid obtained by centrifugation until neutral, and then place it in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC和MoO2组成，其催化性能与实施例7的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide-molybdenum carbide composite material in this example is composed of MoC and MoO 2 , and its catalytic performance is very close to that of the molybdenum dioxide-molybdenum carbide composite material in Example 7.
实施例9：Example 9:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:9:2混合装入球磨罐，并按照球料比10:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1000转/分钟，氩气气氛中球磨2h，再将球磨产物加入质量分数25％的磷酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:9:2 and put them into the ball mill tank, and according to the ball-to-material ratio of 10 : 1 Add the ball milling medium, then add the ball milling tank to the high-energy pendulum ball mill, adjust the ball mill speed to 1000 rpm, ball mill in an argon atmosphere for 2 hours, and then add the ball mill product to a mass fraction of 25% phosphoric acid solution, stir, centrifuge , wash the solid obtained by centrifugation until neutral, and then place it in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC和MoO2组成，其催化性能与实施例7的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide-molybdenum carbide composite material in this example is composed of MoC and MoO 2 , and its catalytic performance is very close to that of the molybdenum dioxide-molybdenum carbide composite material in Example 7.
实施例10：Example 10:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:6:0.3混合装入球磨罐，并按照球料比100:1加入球磨介质，再将球磨罐加入行星式球磨机，调节球磨机转速至400转/分钟，氩气气氛中球磨8h，再将球磨产物加入浓度1mol/L的盐酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:6:0.3 and put them into the ball mill tank, and according to the ball-to-material ratio of 100 : 1 Add the ball milling medium, then add the ball milling jar to the planetary ball mill, adjust the ball mill speed to 400 rpm, ball mill in an argon atmosphere for 8 hours, and then add the ball mill product to a hydrochloric acid solution with a concentration of 1 mol/L, stir, centrifuge, The solid obtained by centrifugation is washed with water until neutral, and then placed in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
性能测试：Performance Testing:
1)本实施例的二氧化钼-碳化钼复合材料的X射线衍射(XRD)图如图5所示。1) The X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of this embodiment is shown in FIG. 5 .
由图5可知：可以观察到MoC、Mo2C和MoO2的特征峰，其中MoC为主相，即本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成。It can be seen from Figure 5 that characteristic peaks of MoC, Mo2C and MoO2 can be observed, wherein MoC is the main phase, that is, the molybdenum dioxide - molybdenum carbide composite material of this embodiment is composed of MoC, Mo2C and MoO2 .
2)本实施例的二氧化钼-碳化钼复合材料在碱性条件(1mol/L的KOH溶液)和酸性条件(0.5mol/L的H2SO4溶液)下的电化学析氢LSV曲线(测试方法同实施例1)依次如图2和图3所示。2) The electrochemical hydrogen evolution LSV curve of the molybdenum dioxide-molybdenum carbide composite material of this embodiment under alkaline conditions (1 mol/L KOH solution) and acidic conditions (0.5 mol/L H 2 SO 4 solution) (test The method is the same as in Example 1) shown in Figure 2 and Figure 3 in turn.
由图2和图3可知：本实施例的二氧化钼-碳化钼复合材料在碱性条件和酸性条件下均展现出优异的催化性能。It can be seen from FIG. 2 and FIG. 3 that the molybdenum dioxide-molybdenum carbide composite material of this embodiment exhibits excellent catalytic performance under both alkaline conditions and acidic conditions.
实施例11：Example 11:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:8:0.3混合装入球磨罐，并按照球料比50:1加入球磨介质，再将球磨罐加入行星式球磨机，调节球磨机转速至400转/分钟，氩气气氛中球磨8h，再将球磨产物加入浓度1mol/L的硫酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:8:0.3 and put them into the ball mill tank, and according to the ball-to-material ratio of 50 : 1 Add the ball milling medium, then add the ball milling jar to the planetary ball mill, adjust the speed of the ball mill to 400 r/min, mill the ball in an argon atmosphere for 8 hours, then add the ball mill product to a sulfuric acid solution with a concentration of 1 mol/L, stir, centrifuge, The solid obtained by centrifugation is washed with water until neutral, and then placed in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成，其催化性能与实施例10的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide-molybdenum carbide composite material of this example is composed of MoC, Mo 2 C and MoO 2 , and its catalytic performance is very close to that of the molybdenum dioxide-molybdenum carbide composite material of Example 10.
实施例12：Example 12:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:9:0.3混合装入球磨罐，并按照球料比20:1加入球磨介质，再将球磨罐加入行星式球磨机，调节球磨机转速至400转/分钟，氩气气氛中球磨8h，再将球磨产物加入质量分数15％的磷酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1 MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:9:0.3 and put them into the ball mill tank, and according to the ball-to-material ratio of 20 : 1 Add the ball milling medium, then add the ball mill jar to the planetary ball mill, adjust the speed of the ball mill to 400 r/min, mill the ball in an argon atmosphere for 8 hours, then add the ball mill product to a phosphoric acid solution with a mass fraction of 15%, stir, centrifuge, The solid obtained by centrifugation is washed with water until neutral, and then placed in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成，其催化性能与实施例10的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide-molybdenum carbide composite material of this example is composed of MoC, Mo 2 C and MoO 2 , and its catalytic performance is very close to that of the molybdenum dioxide-molybdenum carbide composite material of Example 10.
实施例13：Example 13:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:6:1混合装入球磨罐，并按照球料比100:1加入球磨介质，再将球磨罐加入行星式球磨机，调节球磨机转速至500转/分钟，氩气气氛中球磨15h，再将球磨产物加入浓度3mol/L的盐酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon gas until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:6:1 and put them into the ball mill tank, and according to the ball-to-material ratio of 100 : 1 Add the ball milling medium, then add the ball mill jar to the planetary ball mill, adjust the ball mill speed to 500 rpm, ball mill in an argon atmosphere for 15 hours, then add the ball mill product to a 3mol/L hydrochloric acid solution, stir, centrifuge, The solid obtained by centrifugation is washed with water until neutral, and then placed in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
性能测试：Performance Testing:
1)本实施例的二氧化钼-碳化钼复合材料的X射线衍射(XRD)图如图5所示。1) The X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of this embodiment is shown in FIG. 5 .
由图5可知：可以观察到MoC、Mo2C和MoO2的特征峰，其中MoC为主相，即本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成。It can be seen from Figure 5 that characteristic peaks of MoC, Mo2C and MoO2 can be observed, wherein MoC is the main phase, that is, the molybdenum dioxide - molybdenum carbide composite material of this embodiment is composed of MoC, Mo2C and MoO2 .
2)本实施例的二氧化钼-碳化钼复合材料在碱性条件(1mol/L的KOH溶液)和酸性条件(0.5mol/L的H2SO4溶液)下的电化学析氢LSV曲线(测试方法同实施例1)依次如图2和图3所示。2) The electrochemical hydrogen evolution LSV curve of the molybdenum dioxide-molybdenum carbide composite material of this embodiment under alkaline conditions (1 mol/L KOH solution) and acidic conditions (0.5 mol/L H 2 SO 4 solution) (test The method is the same as in Example 1) shown in Figure 2 and Figure 3 in turn.
由图2和图3可知：本实施例的二氧化钼-碳化钼复合材料在碱性条件和酸性条件下均展现出优异的催化性能。It can be seen from FIG. 2 and FIG. 3 that the molybdenum dioxide-molybdenum carbide composite material of this embodiment exhibits excellent catalytic performance under both alkaline conditions and acidic conditions.
实施例14：Example 14:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:8:1混合装入球磨罐，并按照球料比50:1加入球磨介质，再将球磨罐加入行星式球磨机，调节球磨机转速至450转/分钟，氩气气氛中球磨15h，再将球磨产物加入浓度3mol/L的硫酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:8:1 and put them into the ball mill tank, and according to the ball-to-material ratio of 50 : 1 Add the ball milling medium, then add the ball mill jar to the planetary ball mill, adjust the ball mill speed to 450 rpm, ball mill in an argon atmosphere for 15 hours, then add the ball mill product to a 3mol/L sulfuric acid solution, stir, centrifuge, The solid obtained by centrifugation is washed with water until neutral, and then placed in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成，其催化性能与实施例13的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide-molybdenum carbide composite material of this example is composed of MoC, Mo 2 C and MoO 2 , and its catalytic performance is very close to that of the molybdenum dioxide-molybdenum carbide composite material of Example 13.
实施例15：Example 15:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:9:1混合装入球磨罐，并按照球料比20:1加入球磨介质，再将球磨罐加入行星式球磨机，调节球磨机转速至400转/分钟，氩气气氛中球磨15h，再将球磨产物加入质量分数20％的磷酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:9:1 and put them into the ball mill tank, and according to the ball-to-material ratio of 20 : 1 Add the ball milling medium, then add the ball mill tank to the planetary ball mill, adjust the ball mill speed to 400 rpm, ball mill in an argon atmosphere for 15 hours, and then add the ball mill product to a phosphoric acid solution with a mass fraction of 20%, stir, centrifuge, The solid obtained by centrifugation is washed with water until neutral, and then placed in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成，其催化性能与实施例13的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide-molybdenum carbide composite material of this example is composed of MoC, Mo 2 C and MoO 2 , and its catalytic performance is very close to that of the molybdenum dioxide-molybdenum carbide composite material of Example 13.
实施例16：Example 16:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和氮化碳按照摩尔比1:6:1混合装入球磨罐，并按照球料比50:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1230转/分钟，氩气气氛中球磨6h，再将球磨产物加入浓度3mol/L的盐酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon gas until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and carbon nitride in the glove box according to the molar ratio of 1:6:1 and put them into the ball mill jar. Add the ball milling medium at a ratio of 50:1, then add the ball milling jar to the high-energy pendulum ball mill, adjust the speed of the ball mill to 1230 r/min, perform ball milling in an argon atmosphere for 6 hours, and then add the ball milling product to the hydrochloric acid solution with a concentration of 3 mol/L and stir. , centrifuge, wash the solid obtained by centrifugation to neutrality, and then place it in a drying box to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
表征及性能测试：Characterization and performance testing:
本实施例的二氧化钼-碳化钼复合材料的X射线衍射(XRD)图如图6所示。The X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of this embodiment is shown in FIG. 6 .
由图6可知：可以观察到MoC、Mo2C和MoO2的特征峰，即本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成。It can be seen from FIG. 6 that characteristic peaks of MoC, Mo 2 C and MoO 2 can be observed, that is, the molybdenum dioxide-molybdenum carbide composite material of this embodiment is composed of MoC, Mo 2 C and MoO 2 .
实施例17：Example 17:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和氮化碳按照摩尔比1:9:2混合装入球磨罐，并按照球料比50:1加入球磨介质，再将球磨罐加入高能摆振式球磨机，调节球磨机转速至1230转/分钟，氩气气氛中球磨6h，再将球磨产物加入浓度3mol/L的盐酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料。Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and carbon nitride in the glove box according to the molar ratio of 1:9:2 and put them into the ball mill jar. Add the ball milling medium at a ratio of 50:1, then add the ball milling jar to the high-energy pendulum ball mill, adjust the speed of the ball mill to 1230 r/min, perform ball milling in an argon atmosphere for 6 hours, and then add the ball milling product to the hydrochloric acid solution with a concentration of 3 mol/L and stir. , centrifuge, wash the solid obtained by centrifugation to neutrality, and then place it in a drying box to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material.
本实施例的二氧化钼-碳化钼复合材料的X射线衍射(XRD)图如图6所示。The X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of this embodiment is shown in FIG. 6 .
由图6可知：可以观察到MoC和MoO2的特征峰，即本实施例的二氧化钼-碳化钼复合材料由MoC和MoO2组成，其形貌结构和催化性能与实施例16的二氧化钼-碳化钼复合材料十分接近。It can be seen from Figure 6 that the characteristic peaks of MoC and MoO 2 can be observed, that is, the molybdenum dioxide-molybdenum carbide composite material of this example is composed of MoC and MoO 2 , and its morphology, structure and catalytic performance are the same as those of the carbon dioxide in Example 16. Molybdenum-Molybdenum Carbide composites are very close.
实施例18：Example 18:
一种二氧化钼-碳化钼复合材料，其制备方法包括以下步骤：A molybdenum dioxide-molybdenum carbide composite material, the preparation method comprising the following steps:
将氩气充入手套箱直至手套箱内压强为0.1MPa，再在手套箱中将二氧化钼、镁粉和三聚氰胺按照摩尔比1:6:1混合装入球磨罐，并按照球料比100:1加入球磨介质，再将球磨罐加入行星式球磨机，调节球磨机转速至500转/分钟，氩气气氛中球磨15h，再将球磨产物加入浓度3mol/L的盐酸溶液中，搅拌，离心，将离心得到的固体水洗至中性，再置于干燥箱中干燥过夜，即得二氧化钼-碳化钼复合材料Fill the glove box with argon until the pressure in the glove box is 0.1MPa, and then put molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:6:1 and put them into the ball mill tank, and according to the ball-to-material ratio of 100 : 1 Add the ball milling medium, then add the ball mill jar to the planetary ball mill, adjust the ball mill speed to 500 rpm, ball mill in an argon atmosphere for 15 hours, then add the ball mill product to a 3mol/L hydrochloric acid solution, stir, centrifuge, The solid obtained by centrifugation is washed with water until neutral, and then placed in a drying oven to dry overnight to obtain a molybdenum dioxide-molybdenum carbide composite material
经测试，本实施例的二氧化钼-碳化钼复合材料由MoC、Mo2C和MoO2组成，其形貌结构和催化性能与实施例16的二氧化钼-碳化钼复合材料十分接近。After testing, the molybdenum dioxide -molybdenum carbide composite material of this example is composed of MoC, Mo2C and MoO2, and its morphology, structure and catalytic performance are very close to the molybdenum dioxide -molybdenum carbide composite material of Example 16.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, The simplification should be equivalent replacement manners, which are all included in the protection scope of the present invention.
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