技术领域technical field
本发明属于能源材料技术领域，具体涉及一种碳材料负载氟掺杂碳化铌纳米复合材料及其制备方法和应用。The invention belongs to the technical field of energy materials, and in particular relates to a carbon material-loaded fluorine-doped niobium carbide nanocomposite material and a preparation method and application thereof.
背景技术Background technique
由于化石能源的过度开采和使用，全球面临着严峻的能源危机和环境问题，发展新型清洁能源迫在眉睫。燃料电池由于不受卡诺循环，能量转换效率高，受到广泛关注。与氢气相比，液体醇类在生产、储存、运输和使用方面更加便捷，因此直接醇类燃料电池的发展备受瞩目，特别是在新能源汽车领域的应用，受到格外重视。Due to the excessive exploitation and use of fossil energy, the world is facing severe energy crisis and environmental problems, and it is imminent to develop new clean energy. Fuel cells have attracted extensive attention because they are not subject to the Carnot cycle and have high energy conversion efficiency. Compared with hydrogen, liquid alcohols are more convenient in production, storage, transportation and use, so the development of direct alcohol fuel cells has attracted much attention, especially in the field of new energy vehicles.
催化剂作为燃料电池的关键核心组件，对燃料电池的性能与价格具有至关重要的影响。长期以来，燃料电池催化剂主要由Pt族贵金属及其合金构成。然而，铂族贵金属资源稀缺、价格昂贵，严重制约着燃料电池的大规模应用。此外，由于醇氧化反应过程中间产物对Pt具有强烈毒化作用，导致Pt基催化剂稳定性不佳，严重制约长效稳定的直接醇类燃料电池的开发。因此，开发性能优异、价格低廉、原料来源广泛的非贵金属催化剂是燃料电池研究领域的重要努力方向。As a key core component of fuel cells, catalysts have a vital impact on the performance and price of fuel cells. For a long time, fuel cell catalysts are mainly composed of Pt group noble metals and their alloys. However, the scarcity and high price of platinum-group precious metals seriously restrict the large-scale application of fuel cells. In addition, due to the strong poisoning effect on Pt by the intermediate products in the alcohol oxidation reaction, the stability of Pt-based catalysts is poor, which seriously restricts the development of long-term and stable direct alcohol fuel cells. Therefore, the development of non-precious metal catalysts with excellent performance, low price and wide source of raw materials is an important direction of efforts in the field of fuel cell research.
目前为止，例如Fe-N-C、Co-N-C、Zn0.4Ni0.6Co2O4/NCNTs等非贵金属催化剂已经被报道在燃料电池阴极氧还原反应中展现出优异的催化活性，具有重要应用潜力。然而，直接醇类燃料电池阳极非贵金属催化剂的研究进展却鲜有报道，尤其是酸性介质中。因此，开发在酸性介质中具有应用潜力的阳极醇氧化反应非贵金属催化剂，是发展全非贵金属燃料电池全面临的重大挑战和机遇。So far, non-noble metal catalysts such as Fe-NC, Co-NC, Zn0.4 Ni0.6 Co2 O4 /NCNTs have been reported to exhibit excellent catalytic activity in fuel cell cathode oxygen reduction reaction, which has important application potential. However, research progress on non-noble metal catalysts for direct alcohol fuel cell anodes has been rarely reported, especially in acidic media. Therefore, the development of non-noble metal catalysts with potential application in anodic alcohol oxidation reaction in acidic medium is a major challenge and opportunity for the development of all non-noble metal fuel cells.
碳化物具有类铂的电子结构和催化行为。因此，碳化物在许多领域被广泛应用，如Mo2C可作为析氢催化剂，W2C@N,P-C可作为全pH下氢电氧化催化剂等。而杂原子掺杂可以有效地改变材料的电荷密度分布、带隙宽度等电子结构，进而改变其电催化性能。氟具有最大的电负性和最小的原子半径，研究表明氟掺杂可有效改善材料电子结构和催化活性[Adv.Mater.2017,29,1604103]。此前，我们已经报道过氟掺杂纳米碳化钽/石墨化碳复合材料(中国专利CN103977827A)在酸性介质中展现出优异的催化醇的性能，是直接醇类燃料电池阳极催化剂中有潜力的候选者。Carbides have a platinum-like electronic structure and catalytic behavior. Therefore, carbides are widely used in many fields, such as Mo2 C can be used as a hydrogen evolution catalyst, W2 C@N, PC can be used as a hydrogen electrooxidation catalyst at all pH, etc. The heteroatom doping can effectively change the electronic structure of the material such as charge density distribution and band gap width, and then change its electrocatalytic performance. Fluorine has the largest electronegativity and the smallest atomic radius. Studies have shown that fluorine doping can effectively improve the electronic structure and catalytic activity of materials [Adv.Mater.2017,29,1604103]. Previously, we have reported that the fluorine-doped nano-tantalum carbide/graphitized carbon composite material (Chinese patent CN103977827A) exhibits excellent performance in catalyzing alcohols in acidic media, and is a potential candidate for direct alcohol fuel cell anode catalysts.
面对现有的非贵金属燃料电池催化剂较为稀缺的现状，需要开发新的非贵金属燃料电池催化剂。Facing the scarcity of existing non-precious metal fuel cell catalysts, it is necessary to develop new non-precious metal fuel cell catalysts.
发明内容Contents of the invention
本发明的目的在于，克服现有技术中非贵金属燃料电池催化剂稀缺的问题，提供一种新的直接醇类燃料电池阳极非贵金属催化剂——碳材料负载氟掺杂碳化铌纳米复合材料。该材料应用到直接醇类燃料电池中，具有催化醇氧化反应的能力。The purpose of the present invention is to overcome the problem of scarcity of non-precious metal fuel cell catalysts in the prior art, and provide a new direct alcohol fuel cell anode non-precious metal catalyst—a carbon material supported fluorine-doped niobium carbide nanocomposite material. The material is applied to direct alcohol fuel cells and has the ability to catalyze alcohol oxidation reactions.
本发明的另一目的在于，提供上述碳材料负载氟掺杂碳化铌纳米复合材料的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned carbon material-supported fluorine-doped niobium carbide nanocomposite material.
本发明的另一目的在于，提供上述碳材料负载氟掺杂碳化铌纳米复合材料在制备直接醇类燃料电池阳极中的应用。Another object of the present invention is to provide the application of the above-mentioned carbon material-supported fluorine-doped niobium carbide nanocomposite material in the preparation of direct alcohol fuel cell anodes.
为实现上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种碳材料负载氟掺杂碳化铌纳米复合材料，氟掺杂碳化铌负载在碳材料上；碳化铌的负载量为10～70wt％，氟掺杂量为碳化铌的0.1～5mol％。A carbon material loaded fluorine-doped niobium carbide nanocomposite material, the fluorine-doped niobium carbide is loaded on the carbon material;
本发明通过大量研究发现，如将具有氯化钠晶型(六方晶型)结构的碳化铌晶体负载到碳材料上，形成特定的的碳材料负载碳化铌纳米复合材料，同时将一定量的氟元素掺杂到碳化铌晶体中，可以使得该复合材料作为燃料电池的阳极催化剂，具有很好的催化醇氧化反应的能力，提高燃料电池的电化学性能(如峰电流)。Through extensive research, the present invention finds that if niobium carbide crystals having a sodium chloride crystal form (hexagonal crystal form) structure are loaded onto carbon materials to form specific carbon material-loaded niobium carbide nanocomposites, and a certain amount of fluorine is doped into the niobium carbide crystals, the composite material can be used as an anode catalyst for a fuel cell, which has a good ability to catalyze alcohol oxidation reactions and improve the electrochemical performance (such as peak current) of the fuel cell.
优选地，碳化铌的负载量为10～40wt％，氟掺杂量为碳化铌的0.5～1mol％。Preferably, the loading amount of niobium carbide is 10-40 wt%, and the doping amount of fluorine is 0.5-1 mol% of the niobium carbide.
优选地，所述碳材料石墨化碳。Preferably, the carbon material is graphitized carbon.
所述碳材料负载氟掺杂碳化铌纳米复合材料的制备方法，包括如下步骤：The preparation method of the carbon material-loaded fluorine-doped niobium carbide nanocomposite material comprises the following steps:
S1.碳源经预处理后得到具有活性位点的碳前驱体；S1. The carbon source is pretreated to obtain a carbon precursor with active sites;
S2.铌源、氟源在溶剂中混合均匀后得到前驱体溶液；S2. The niobium source and the fluorine source are uniformly mixed in a solvent to obtain a precursor solution;
S3.将S1.得到的碳前驱体加入到S2.的前驱体溶液中混合均匀，得到碳前驱体-铌-氟中间吸附产物；S3. Add the carbon precursor obtained in S1. to the precursor solution in S2. and mix evenly to obtain a carbon precursor-niobium-fluorine intermediate adsorption product;
S4.S3.得到的碳前驱体-铌-氟中间吸附产物在60～120℃下反应得到中间产物；S4.S3. The obtained carbon precursor-niobium-fluorine intermediate adsorption product is reacted at 60-120°C to obtain an intermediate product;
S5.S4.得到的中间产物干燥处理后，在保护气氛中1000～1500℃下进行热处理30～120min，即得到所述碳材料负载氟掺杂碳化铌纳米复合材料。S5.S4. After the obtained intermediate product is dried, heat treatment is carried out at 1000-1500° C. for 30-120 minutes in a protective atmosphere to obtain the carbon material-supported fluorine-doped niobium carbide nanocomposite material.
优选地，步骤S1.中所述碳源为碳粉、碳布、多壁碳纳米管、泡沫碳、氧化石墨烯、阴离子交换树脂、阳离子交换树脂或两性离子交换树脂中的一种或几种的组合。Preferably, the carbon source in step S1. is one or a combination of carbon powder, carbon cloth, multi-walled carbon nanotubes, carbon foam, graphene oxide, anion exchange resin, cation exchange resin or amphoteric ion exchange resin.
不同形式的碳源在比表面积以及对碳化铌的合成、氟元素的掺杂、催化剂整体稳定性等性能方面会有差异，进而影响制备得到的复合材料的电催化性能。Different forms of carbon sources will have differences in the specific surface area, the synthesis of niobium carbide, the doping of fluorine elements, and the overall stability of the catalyst, which will affect the electrocatalytic performance of the prepared composite materials.
为了进一步提高复合材料的电催化性，进一步优选地，步骤S1.中所述碳源为氧化石墨烯、多壁碳纳米管或苯乙烯阴离子树脂中的一种或几种的组合。In order to further improve the electrocatalytic performance of the composite material, it is further preferred that the carbon source in step S1. is one or a combination of graphene oxide, multi-walled carbon nanotubes or styrene anion resins.
更进一步优选地，步骤S1.中所述碳源为氧化石墨烯。Still further preferably, the carbon source in step S1. is graphene oxide.
需要说明的是，不同形式的碳源经过上述制备过程后，在最终产品中均转变为石墨化碳。It should be noted that, after the above-mentioned preparation process, different forms of carbon sources are transformed into graphitized carbon in the final product.
优选地，当S1.中所述碳源为碳粉、碳布、多壁碳纳米管、泡沫碳或氧化石墨烯中的一种或几种的组合时，所述预处理为水热处理，水热处理的条件为：碳材料加入30～70wt％的HNO3水溶液中，在60～120℃下处理6～12h。Preferably, when the carbon source in S1. is one or a combination of carbon powder, carbon cloth, multi-walled carbon nanotubes, foamed carbon or graphene oxide, the pretreatment is hydrothermal treatment, and the conditions for hydrothermal treatment are: carbon materials are added to 30-70 wt%HNO3 aqueous solution, and treated at 60-120°C for 6-12 hours.
优选地，所述水热处理后的产物用去离子水清洗，并真空干燥4～24h。Preferably, the product after the hydrothermal treatment is washed with deionized water and dried in vacuum for 4-24 hours.
优选地，当S1.中所述碳源为阴离子交换树脂、阳离子交换树脂或两性离子交换树脂中的一种或几种组合时，所述预处理为酸碱处理法或次氯酸盐处理法中的一种或两种的组合。Preferably, when the carbon source in S1. is one or a combination of anion exchange resin, cation exchange resin or amphoteric ion exchange resin, the pretreatment is one or a combination of acid-base treatment or hypochlorite treatment.
优选地，所述阴离子交换树脂为大孔碱性丙烯酸系阴离子交换树脂或碱性苯乙烯系阴离子交换树脂中的一种或几种的组合；所述阳离子交换树脂为强酸型阳离子交换树脂或弱酸型阳离子交换树脂中的一种或几种的组合；所述两性离子交换树脂为丙烯酸-苯乙烯系两性离子交换树脂。Preferably, the anion exchange resin is a combination of one or more of macroporous basic acrylic anion exchange resins or basic styrene anion exchange resins; the cation exchange resin is a combination of one or more of strong acid cation exchange resins or weak acid cation exchange resins; and the amphoteric ion exchange resin is acrylic-styrene amphoteric ion exchange resins.
优选地，所述酸碱处理法按照《GB/T 5476-1996》标准进行处理。Preferably, the acid-base treatment method is carried out according to the "GB/T 5476-1996" standard.
优选地，所述铌源为草酸铌、氯化铌、七氟铌酸钾、乙醇铌或铌酸钾中的一种或几种的组合。Preferably, the niobium source is one or a combination of niobium oxalate, niobium chloride, potassium heptafluoroniobate, niobium ethoxide or potassium niobate.
优选地，所述氟源为七氟铌酸钾、氟化钾、氟化钠、氟化铵或四丁基氟化铵中的一种或几种的组合。Preferably, the fluorine source is one or a combination of potassium heptafluoroniobate, potassium fluoride, sodium fluoride, ammonium fluoride or tetrabutylammonium fluoride.
优选地，铌源中铌元素与碳源的摩尔质量比为0.0005～0.01mol/g。Preferably, the molar mass ratio of niobium element to carbon source in the niobium source is 0.0005˜0.01 mol/g.
优选地，氟源中氟元素与铌源中铌元素的摩尔比为1:5～10:1。Preferably, the molar ratio of the fluorine element in the fluorine source to the niobium element in the niobium source is 1:5˜10:1.
优选地，S2.或S3.中所述混合的方式为搅拌或超声处理。Preferably, the mixing method in S2. or S3. is stirring or ultrasonic treatment.
优选地，S4.中所述反应的方式为微波水热反应、微波溶剂热反应、普通水热反应、普通溶剂热反应、机械搅拌水浴反应、磁力搅拌水热反应、磁力搅拌溶剂热反应中的任一种。Preferably, the reaction method in S4. is any one of microwave hydrothermal reaction, microwave solvothermal reaction, ordinary hydrothermal reaction, ordinary solvothermal reaction, mechanical stirring water bath reaction, magnetic stirring hydrothermal reaction, and magnetic stirring solvothermal reaction.
优选地，所述溶剂为水或硝酸中的一种或两种的组合。Preferably, the solvent is one or a combination of water or nitric acid.
优选地，当S4.中所述反应的方式为机械搅拌水热反应或磁力搅拌水热反应时，搅拌的转速为200～800rpm。Preferably, when the reaction described in S4. is mechanical stirring hydrothermal reaction or magnetic stirring hydrothermal reaction, the stirring speed is 200-800 rpm.
优选地，S4.中所述反应的时间为6～12h。Preferably, the reaction time in S4. is 6-12 hours.
优选地，S5.中所述干燥为真空干燥、鼓风干燥或冷冻干燥中的一种或几种的组合。Preferably, the drying described in S5. is one or a combination of vacuum drying, blast drying or freeze drying.
优选地，S5.中所述干燥的时间为10～80h。Preferably, the drying time described in S5. is 10-80 hours.
优选地，S5.中所述保护气氛为甲烷、氢气、一氧化碳、氩气或氮气中的一种或几种气体组成的气氛。Preferably, the protective atmosphere in S5. is an atmosphere composed of one or more of methane, hydrogen, carbon monoxide, argon or nitrogen.
优选地，S5.中所述气体的流量为20～100cc/min；进一步优选为20～80cc/min。Preferably, the flow rate of the gas described in S5. is 20-100 cc/min; more preferably 20-80 cc/min.
优选地，S5.中所述热处理在管式炉或箱式炉中进行。Preferably, the heat treatment described in S5. is performed in a tube furnace or a box furnace.
优选地，S5.中所述热处理的升温速率为1～10℃/min。Preferably, the heating rate of the heat treatment in S5. is 1-10° C./min.
进一步优选地，S5.中所述热处理的升温速率为2～8℃/min。Further preferably, the heating rate of the heat treatment in S5. is 2-8°C/min.
优选地，S5.中所述热处理的时间为40～100min。Preferably, the heat treatment time in S5. is 40-100 min.
优选地，S5.中所述热处理的温度为1000～1300℃。Preferably, the heat treatment temperature in S5. is 1000-1300°C.
优选地，S5.中还包括后处理，所述后处理为研磨、洗涤和干燥。Preferably, post-processing is also included in S5. The post-processing is grinding, washing and drying.
本发明上述的制备方法，成本低廉，原料来源广泛，在相对较低的温度下合成碳材料负载氟掺杂碳化铌纳米复合材料，且工艺简便、制备快速、安全、环保、易于实现产业化生产。The above-mentioned preparation method of the present invention has low cost and wide sources of raw materials, and can synthesize carbon material-loaded fluorine-doped niobium carbide nanocomposite materials at a relatively low temperature, and has simple process, rapid preparation, safety, environmental protection, and easy realization of industrialized production.
上述碳材料负载氟掺杂碳化铌纳米复合材料在制备燃料电池中的应用也在本发明的保护范围内。The application of the above-mentioned carbon material-supported fluorine-doped niobium carbide nanocomposite material in the preparation of fuel cells is also within the protection scope of the present invention.
所述燃料电池的介质为酸性介质或者碱性介质。The medium of the fuel cell is an acidic medium or an alkaline medium.
优选地，所述酸性介质为硫酸、高氯酸或磷酸中的一种或几种的组合；所述碱性介质为氢氧化钾。Preferably, the acidic medium is one or a combination of sulfuric acid, perchloric acid or phosphoric acid; the alkaline medium is potassium hydroxide.
优选地，所述酸性介质或者碱性介质的浓度为0.1～5mol/L，进一步优选为0.5～3mol/L.Preferably, the concentration of the acidic medium or alkaline medium is 0.1-5 mol/L, more preferably 0.5-3 mol/L.
优选地，所述燃料电池的燃料为甲醇或乙醇。Preferably, the fuel of the fuel cell is methanol or ethanol.
优选地，所述燃料的浓度为0.1～5mol/L，进一步优选为1～5mol/L。Preferably, the concentration of the fuel is 0.1-5 mol/L, more preferably 1-5 mol/L.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
本发明将铌元素和氟元素负载到碳材料中，形成的碳材料负载氟掺杂碳化铌纳米复合材料，应用到直接醇类燃料电池中，具有催化醇氧化反应的能力，可以显著提高燃料电池的电化学性能(如峰电流)。The present invention loads niobium and fluorine into carbon materials, and the formed carbon material supports fluorine-doped niobium carbide nanocomposites, which are applied to direct alcohol fuel cells, have the ability to catalyze alcohol oxidation reactions, and can significantly improve the electrochemical performance (such as peak current) of fuel cells.
附图说明Description of drawings
图1为实施例1制备得到的碳材料负载氟掺杂碳化铌纳米复合材料的XRD谱图；Fig. 1 is the XRD spectrogram of the carbon material loaded fluorine-doped niobium carbide nanocomposite material prepared in Example 1;
图2为实施例1制备得到的碳材料负载氟掺杂碳化铌纳米复合材料催化甲醇燃料电池的循环伏安曲线图。FIG. 2 is a cyclic voltammetry curve of the carbon material-supported fluorine-doped niobium carbide nanocomposite material prepared in Example 1 to catalyze a methanol fuel cell.
具体实施方式Detailed ways
以下结合具体实施例和附图来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。除非特别说明，本发明所用试剂和材料均为市购。The present invention will be further described below in conjunction with specific embodiments and drawings, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field. Unless otherwise specified, the reagents and materials used in the present invention are commercially available.
实施例1Example 1
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，由包括如下步骤得方法制备得到：This embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material, which is prepared by a method comprising the following steps:
S1.将200mg的氧化石墨烯置于40mL的70％的HNO3溶液中进行超声处理30min，随即将混合物转移至聚四氟乙烯反应釜中，并在90℃下进行水热反应8h；随后用去离子水对反应产物进行清洗处理，抽滤后，真空干燥12h，得到碳前驱体；S1. Put 200 mg of graphene oxide in 40 mL of 70%HNO3 solution for ultrasonic treatment for 30 min, then transfer the mixture to a polytetrafluoroethylene reactor, and conduct a hydrothermal reaction at 90 ° C for 8 h; then wash the reaction product with deionized water, filter it with suction, and dry it in vacuum for 12 h to obtain a carbon precursor;
S2.将72.6mg七氟铌酸钾置于100mL的聚四氟乙烯内衬中，并加入60mL去离子水，超声处理30min得到前驱体溶液；S2. Place 72.6mg of potassium heptafluoroniobate in a 100mL polytetrafluoroethylene liner, add 60mL of deionized water, and perform ultrasonic treatment for 30 minutes to obtain a precursor solution;
S3.将S1.得到的碳前驱体加入到S2.的前驱体溶液中，超声处理30min，得到碳前驱体-铌-氟中间吸附产物；S3. Add the carbon precursor obtained in S1. to the precursor solution in S2., and ultrasonically treat it for 30 minutes to obtain a carbon precursor-niobium-fluorine intermediate adsorption product;
S4.S3.得到的装有碳前驱体-铌-氟中间吸附产物的聚四氟乙烯内衬装入反应釜中，在90℃下搅拌反应10h，搅拌转速为600rpm，得到中间产物；S4.S3. The obtained polytetrafluoroethylene liner containing the carbon precursor-niobium-fluorine intermediate adsorption product was put into the reaction kettle, and stirred and reacted at 90°C for 10 hours at a stirring speed of 600rpm to obtain the intermediate product;
S5.S4.反应后的水溶液转移至离心管中，冷冻后进行冷冻干燥48h；干燥后的样品置于管式炉中在流量为20cc/min的甲烷/氢气气氛下以5℃/min的升温速率升至1000℃并保持30min后，将热处理后的样品研磨至分散，用去离子水洗涤，然后在室温下干燥，得到还原氧化石墨烯负载氟掺杂碳化铌纳米复合材料。S5.S4. After the reaction, the aqueous solution was transferred to a centrifuge tube, and then freeze-dried for 48 hours; the dried sample was placed in a tube furnace and raised to 1000°C at a rate of 5°C/min under a methane/hydrogen atmosphere with a flow rate of 20cc/min and maintained for 30min.
制备得到的还原氧化石墨烯负载氟掺杂碳化铌纳米复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～1mol％(需要说明的是，本实施例中氟元素采用电感耦合等离子体质谱(ICP-MS)进行测试得到，在测试过程中氟元素会随着温度的变化，在材料中移动或蒸发，因此，得到的氟元素的含量是一个范围)。In the prepared reduced graphene oxide-supported fluorine-doped niobium carbide nanocomposite material, the loading amount of niobium carbide is 10wt%, and the fluorine doping amount is 0.5-1mol% of the niobium carbide (it should be noted that in this embodiment, the fluorine element is tested by inductively coupled plasma mass spectrometry (ICP-MS). During the test, the fluorine element will move or evaporate in the material as the temperature changes. Therefore, the obtained fluorine element content is within a range).
实施例2Example 2
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S2.中七氟铌酸钾的用量为163.6mg。This example provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that the amount of potassium heptafluoroniobate in S2. is 163.6 mg.
制备得到的复合材料中，碳化铌的负载量为20wt％，氟掺杂量为碳化铌的0.5～3mol％。In the prepared composite material, the loading amount of niobium carbide is 20wt%, and the doping amount of fluorine is 0.5-3mol% of the niobium carbide.
实施例3Example 3
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S2.中七氟铌酸钾的用量为280.5mg。This example provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that the dosage of potassium heptafluoroniobate in S2. is 280.5 mg.
制备得到的复合材料中，碳化铌的负载量为30wt％，氟掺杂量为碳化铌的0.5～4mol％。In the prepared composite material, the loading amount of niobium carbide is 30wt%, and the doping amount of fluorine is 0.5-4mol% of the niobium carbide.
实施例4Example 4
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S2.中七氟铌酸钾的用量为304.9mg。This example provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that the dosage of potassium heptafluoroniobate in S2. is 304.9 mg.
制备得到的复合材料中，碳化铌的负载量为40wt％，氟掺杂量为碳化铌的1.5～5mol％。In the prepared composite material, the loading amount of niobium carbide is 40wt%, and the doping amount of fluorine is 1.5-5mol% of the niobium carbide.
实施例5Example 5
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S2.中72.6mg七氟铌酸钾替换为249.26mg氯化铌和514.89mg氟化钠。This example provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that 72.6 mg of potassium heptafluoroniobate in S2. is replaced by 249.26 mg of niobium chloride and 514.89 mg of sodium fluoride.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～4mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-4mol% of the niobium carbide.
实施例6Example 6
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S4.中反应的温度为80℃。This example provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that the reaction temperature in S4. is 80°C.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～3mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-3mol% of the niobium carbide.
实施例7Example 7
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S4.中反应的温度为100℃。This example provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that the reaction temperature in S4. is 100°C.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～4mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-4mol% of the niobium carbide.
实施例8Example 8
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S4.中反应的时间为11h。This example provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that the reaction time in S4. is 11 hours.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～5mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-5mol% of the niobium carbide.
实施例9Example 9
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S5.中热处理的时间为120min。This example provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that the heat treatment time in S5. is 120 minutes.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～5mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-5mol% of the niobium carbide.
实施例10Example 10
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S5.中热处理的温度为1200℃。This embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and the embodiment 1 is that the heat treatment temperature in S5. is 1200°C.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～2mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-2mol% of the niobium carbide.
实施例11Example 11
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S5.中，管式炉中保护气氛为氩气/氢气混合气气氛。This embodiment provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and the embodiment 1 is that in S5., the protective atmosphere in the tube furnace is an argon/hydrogen gas mixture atmosphere.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～2mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-2mol% of the niobium carbide.
实施例12Example 12
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S5.中，管式炉中保护气氛为甲烷。This embodiment provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and the embodiment 1 is that in S5., the protective atmosphere in the tube furnace is methane.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～2mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-2mol% of the niobium carbide.
实施例13Example 13
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S5.中，甲烷/氢气流量为40cc/min。This embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and the embodiment 1 is that in S5., the flow rate of methane/hydrogen is 40 cc/min.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～3mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-3mol% of the niobium carbide.
实施例14Example 14
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S5.中，甲烷/氢气流量为100cc/min。This embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and the embodiment 1 is that in S5., the flow rate of methane/hydrogen is 100 cc/min.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～2mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-2mol% of the niobium carbide.
实施例15Example 15
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S1.中碳源为碳粉；S5.中得到还原碳粉负载氟掺杂碳化铌纳米复合材料。This example provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that in S1. the carbon source is carbon powder; in S5. the reduced carbon powder-supported fluorine-doped niobium carbide nanocomposite material is obtained.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～3mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-3mol% of the niobium carbide.
实施例16Example 16
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S1.中碳源为多壁碳纳米管；S5.中得到还原碳布负载氟掺杂碳化铌纳米复合材料。This example provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that the carbon source in S1. is a multi-walled carbon nanotube; in S5., a reduced carbon cloth-loaded fluorine-doped niobium carbide nanocomposite material is obtained.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～3mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-3mol% of the niobium carbide.
实施例17Example 17
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S1.中碳源为碳布；S5.中得到还原碳布负载氟掺杂碳化铌纳米复合材料。This example provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that in S1. the carbon source is carbon cloth; in S5. the reduced carbon cloth-loaded fluorine-doped niobium carbide nanocomposite material is obtained.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～3mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-3mol% of the niobium carbide.
实施例18Example 18
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S1.中碳源为泡沫碳；S5.中得到还原泡沫碳负载氟掺杂碳化铌纳米复合材料。This example provides a carbon material-supported fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that the carbon source in S1. is carbon foam; in S5., the reduced foam carbon-supported fluorine-doped niobium carbide nanocomposite material is obtained.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～3mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-3mol% of the niobium carbide.
实施例19Example 19
本实施例提供一种碳材料负载氟掺杂碳化铌纳米复合材料，其制备方法与实施例1的不同之处在于，S1.中碳源为苯乙烯阴离子树脂，按照《GB/T 5476-1996》标准对苯乙烯阴离子树脂进行预处理；S5.中得到石墨化碳负载氟掺杂碳化铌纳米复合材料。This example provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite material. The difference between its preparation method and Example 1 is that the carbon source in S1. is a styrene anion resin, and the styrene anion resin is pretreated according to the "GB/T 5476-1996" standard; in S5., a graphitized carbon-loaded fluorine-doped niobium carbide nanocomposite material is obtained.
制备得到的复合材料中，碳化铌的负载量为10wt％，氟掺杂量为碳化铌的0.5～3mol％。In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the doping amount of fluorine is 0.5-3mol% of the niobium carbide.
对上述实施例制备得到的碳材料负载氟掺杂碳化铌纳米复合材料进行性能测试：The performance test of the carbon material loaded fluorine-doped niobium carbide nanocomposite prepared in the above examples:
1.对上述实施例制备的得到的碳材料负载氟掺杂碳化铌纳米复合材料选用X射线衍射仪进行结构表征，结果如图1所示；1. Select X-ray diffractometer to carry out structural characterization of the carbon material-loaded fluorine-doped niobium carbide nanocomposite prepared in the above-mentioned embodiments, and the results are shown in Figure 1;
2.将上述实施例制备得到的碳材料负载氟掺杂碳化铌纳米复合材料置于酸性(1mol/L甲醇+0.5mol/L硫酸混合溶液)环境中进行电化学测试，其中在30℃下、50mV/s的速度进行扫描，得到的循环伏安曲线图如图2以及表1所示。2. The carbon material-loaded fluorine-doped niobium carbide nanocomposite prepared in the above examples was placed in an acidic (1mol/L methanol+0.5mol/L sulfuric acid mixed solution) environment for electrochemical testing, wherein scanning was performed at a speed of 50mV/s at 30°C, and the obtained cyclic voltammetry curves were shown in Figure 2 and Table 1.
表1实施例以及对比例制备得到的纳米复合材料电化学性能测试结果Table 1 embodiment and the nanocomposite electrochemical performance test result that comparative example prepares
从图1可以看出，实施例1制备得到的复合材料中含有石墨碳以及碳化铌的峰，且与碳化铌标准样品对比发现，复合材料中的碳化铌的各个峰(峰位置：34.7、40.4、58.5、69.8、73.5、87.2)与标准碳化铌(标准峰:34.7、40.3、58.3、69.7、73.3、87.1)相比有一点偏移，表明成功合成了碳材料负载氟掺杂碳化铌纳米复合材料。其它实施例制备得到的复合材料的XRD图谱与实施例1类似。As can be seen from Figure 1, the composite material prepared in Example 1 contains peaks of graphite carbon and niobium carbide, and compared with the niobium carbide standard sample, it is found that each peak (peak position: 34.7, 40.4, 58.5, 69.8, 73.5, 87.2) of the niobium carbide in the composite material has a little shift compared with the standard niobium carbide (standard peak: 34.7, 40.3, 58.3, 69.7, 73.3, 87.1) , indicating the successful synthesis of carbon material-supported fluorine-doped niobium carbide nanocomposites. The XRD pattern of the composite material prepared in other examples is similar to Example 1.
图2为实施例1制备得到的碳材料负载氟掺杂碳化铌纳米复合材料在酸性条件下催化甲醇燃料电池的循环伏安曲线图，从图中可以看出，峰电流为2.7mA，峰电位1.1V，表明该复合材料用在燃料电池中作为阳极催化剂具有很好的催化活性，尤其具有较大的峰电流。其它实施例的电化学性能如表1所示，可以看出，本发明各实施例制备得到的碳材料负载氟掺杂碳化铌纳米复合材料具有很好的催化活性。另外，从实施例1以及实施例15～19的对比可以看出，选取不同的碳源，制备得到的燃料电池的电催化性能(尤其是峰电流)具有一定的差异，其中氧化石墨烯、多壁碳纳米管以及苯乙烯阴离子树脂作为碳源，制备得到的燃料电池的峰电流较大，其中氧化石墨烯为碳源制备得到的燃料电池的峰电流最大。Fig. 2 is the cyclic voltammetry curve of the fluorine-doped niobium carbide nanocomposite material loaded on carbon material prepared in Example 1 under acidic conditions to catalyze the methanol fuel cell. As can be seen from the figure, the peak current is 2.7mA and the peak potential is 1.1V, indicating that the composite material has good catalytic activity when used as an anode catalyst in a fuel cell, especially with a relatively large peak current. The electrochemical properties of other examples are shown in Table 1. It can be seen that the carbon material-supported fluorine-doped niobium carbide nanocomposites prepared in each example of the present invention have good catalytic activity. In addition, from the comparison of Example 1 and Examples 15-19, it can be seen that the electrocatalytic performance (especially the peak current) of the prepared fuel cells has certain differences when different carbon sources are selected. Among them, graphene oxide, multi-walled carbon nanotubes and styrene anion resin are used as the carbon source, and the peak current of the prepared fuel cell is relatively large, and the peak current of the fuel cell prepared by using graphene oxide as the carbon source is the largest.
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above-mentioned specific implementation manners further describe the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above-mentioned descriptions are only specific implementation modes of the present invention, and are not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
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| CN202110781718.9ACN113644284B (en) | 2021-07-08 | 2021-07-08 | A carbon material-loaded fluorine-doped niobium carbide nanocomposite material and its preparation method and application |
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| CN202110781718.9ACN113644284B (en) | 2021-07-08 | 2021-07-08 | A carbon material-loaded fluorine-doped niobium carbide nanocomposite material and its preparation method and application |
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