技术领域technical field
本发明属于催化剂材料技术领域，更具体地，涉及一种以Ce-MOF为前驱体的二氧化铈/氮化钛纳米管(CeO2/TiN NTs)及其制备方法和应用。The invention belongs to the technical field of catalyst materials, and more specifically relates to a cerium oxide/titanium nitride nanotube (CeO2 /TiN NTs) with Ce-MOF as a precursor and a preparation method and application thereof.
背景技术Background technique
氮化钛(TiN)是一种立方晶系结晶，其具有高硬度、高熔点及高温化学稳定性等特点，是良好的导电、导热体。相对于零维的氮化钛颗粒，中空和多孔的一维的氮化钛纳米管(TiN NTs)具有更大的比表面积，提高了反应过程中的传质速率。由于纳米管之间的相互作用，导电性能得到较大提高，有利于电子的传导。以氮化钛纳米管为载体的研究也有相关的报道。赵凤鸣等人(赵峰鸣,闻刚,孔丽瑶,等.氮化钛纳米管作为钒电池负极对V(Ⅱ)/V(Ⅲ)的电化学性能[J].无机化学学报,2017,33(3):501-508.)研究后发现氮化钛大的比表面积和快速的电子通道对V(Ⅱ)/V(Ⅲ)展现了优异的电催化活性和可逆性。段昊男等人(段昊男,陈韬,刘金科,等.氮化钛-碳纳米管复合载体负载铂催化剂的催化活性与稳定性研究[J].化工新型材料,2017(9):175-177.)研究后发现氮化钛可增强贵金属Pt与载体之间的相互作用，且以TiN-CNTs为载体的催化剂表现更高的稳定性和催化活性。Titanium nitride (TiN) is a cubic crystal system, which has the characteristics of high hardness, high melting point and high temperature chemical stability, and is a good electrical and thermal conductor. Compared with zero-dimensional TiN particles, the hollow and porous one-dimensional TiN nanotubes (TiN NTs) have a larger specific surface area, which improves the mass transfer rate during the reaction. Due to the interaction between nanotubes, the electrical conductivity is greatly improved, which is conducive to the conduction of electrons. There are also related reports on the research on titanium nitride nanotubes as the carrier. Zhao Fengming et al. (Zhao Fengming, Wen Gang, Kong Liyao, et al. Electrochemical performance of titanium nitride nanotubes as negative electrode pair V(Ⅱ)/V(Ⅲ) in vanadium batteries[J]. Journal of Inorganic Chemistry, 2017,33(3 ):501-508.) After the study, it was found that the large specific surface area and fast electron channel of titanium nitride exhibited excellent electrocatalytic activity and reversibility for V(Ⅱ)/V(Ⅲ). Duan Haonan et al. (Duan Haonan, Chen Tao, Liu Jinke, et al. Study on Catalytic Activity and Stability of Titanium Nitride-Carbon Nanotube Composite Support Supported Platinum Catalyst[J]. New Chemical Materials, 2017(9):175-177.) After the study, it was found that titanium nitride can enhance the interaction between the noble metal Pt and the support, and the catalyst based on TiN-CNTs showed higher stability and catalytic activity.
金属有机框架(MOFs)以其丰富多样的结构、高比表面积、高孔隙率等优点，在气体吸附、催化等领域被广为推广应用。CeO2因其突出的储氧能力和氧化还原能力，在环境催化领域迅速发展起来。以MOF为前驱体制备的多孔催化剂载体在性能上有很大提高。专利CN107824177 A介绍一种以Ce-MOF为铈前驱体的CeO2/TiO2低温SCR催化剂的制备方法，制备出了对氨选择性催化还原具有高催化活性的催化剂。专利CN 106955742 A介绍了一种Ce-MOF光催化材料的制备方法及应用，其成功制备了一种Ce-MOF光催化材料，具有较好的光学特性和良好的热稳定性，反应条件温和且不造成二次污染。Metal-organic frameworks (MOFs) are widely used in the fields of gas adsorption and catalysis due to their rich and diverse structures, high specific surface area, and high porosity. CeO2 has rapidly developed in the field of environmental catalysis due to its outstanding oxygen storage capacity and redox ability. Porous catalyst supports prepared from MOF precursors have greatly improved performance. Patent CN107824177 A introduces a preparation method of CeO2 /TiO2 low-temperature SCR catalyst using Ce-MOF as cerium precursor, and prepares a catalyst with high catalytic activity for selective catalytic reduction of ammonia. Patent CN 106955742 A introduces the preparation method and application of a Ce-MOF photocatalytic material, which successfully prepared a Ce-MOF photocatalytic material, which has good optical properties and good thermal stability, and the reaction conditions are mild and No secondary pollution will be caused.
目前，以Ce-MOF为前驱体制备出来的催化剂基本上都是负载在TiO2或者碳黑上，负载在TiN纳米管状结构还未见相关报道。At present, the catalysts prepared with Ce-MOF as the precursor are basically supported on TiO2 or carbon black, and there is no related report on the TiN nanotube structure.
发明内容Contents of the invention
为了解决上述现有技术存在的不足和缺点，提供一种以Ce-MOF为前驱体的二氧化铈/氮化钛纳米管。In order to solve the deficiencies and shortcomings of the above-mentioned prior art, a cerium oxide/titanium nitride nanotube with Ce-MOF as a precursor is provided.
本发明的另一目的在于提供上述以Ce-MOF为前驱体的二氧化铈/氮化钛纳米管的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned ceria/titanium nitride nanotubes using Ce-MOF as a precursor.
本发明的再一目的在于提供上述以Ce-MOF为前驱体的二氧化铈/氮化钛纳米管的应用。Another object of the present invention is to provide the application of the above-mentioned ceria/titanium nitride nanotubes with Ce-MOF as precursor.
本发明的目的通过下述技术方案来实现：The purpose of the present invention is achieved through the following technical solutions:
一种以Ce-MOF为前驱体的二氧化铈/氮化钛纳米管，所述二氧化铈/氮化钛纳米管(CeO2/TiN NTs)是将Ce-MOF前驱框架和钛源溶于溶剂中，并加入到高压反应釜中，在110～200℃下进行反应，反应结束后冷却、过滤、洗涤、干燥，再经过煅烧后，进行后氮化处理制得。A ceria/titanium nitride nanotube with Ce-MOF as precursor, the ceria/titanium nitride nanotube (CeO2 /TiN NTs) is the Ce-MOF precursor framework and titanium source dissolved in Solvent, and added to the high-pressure reactor, react at 110 ~ 200 ° C, after the reaction is cooled, filtered, washed, dried, and then after calcination, post-nitridation treatment is obtained.
优选地，所述的Ce-MOF前驱框架是将铈源和有机羧酸配体溶解在有机溶剂中，过滤后经真空干燥制得。Preferably, the Ce-MOF precursor framework is prepared by dissolving a cerium source and an organic carboxylic acid ligand in an organic solvent, filtering and drying in a vacuum.
更为优选地，所述铈源为醋酸铈、七水合硝酸铈或六水合硝酸铈中的一种以上，所述有机羧酸配体为对苯二甲酸、草酸、2-吡啶甲酸、丙二酸、均苯三酸或柠檬酸中的一种以上，所述有机溶剂为甲醇、乙醇、二甲基亚砜或二丙基甲酰胺中的一种以上，所述铈源和有机羧酸配体的物质的量比为(1～10)：1；所述铈源和有机羧酸配体总的质量与有机溶剂的体积比为(0.005～0.050)g:1mL。More preferably, the cerium source is one or more of cerium acetate, cerium nitrate heptahydrate, or cerium nitrate hexahydrate, and the organic carboxylic acid ligand is terephthalic acid, oxalic acid, 2-pyridinecarboxylic acid, propanedi acid, trimesic acid or citric acid, the organic solvent is more than one of methanol, ethanol, dimethyl sulfoxide or dipropyl formamide, the cerium source and the organic carboxylic acid complex The material ratio of the body is (1-10):1; the volume ratio of the total mass of the cerium source and the organic carboxylic acid ligand to the organic solvent is (0.005-0.050) g:1 mL.
优选地，所述钛源为硫酸氧钛、钛酸四乙酯、钛酸四丁酯或钛酸四戊酯中的一种以上，所述溶剂为无水乙醇、丁二醇和丁醚。Preferably, the titanium source is one or more of titanyl sulfate, tetraethyl titanate, tetrabutyl titanate or tetrapentyl titanate, and the solvent is absolute ethanol, butylene glycol and butyl ether.
优选地，所述无水乙醇、丁二醇和丁醚的体积比为2：1：1。Preferably, the volume ratio of the absolute ethanol, butanediol and butyl ether is 2:1:1.
优选地，所述煅烧的温度为250～550℃，所述煅烧的时间为3～6h；所述后氮化处理的温度为650～800℃，后氮化处理的的时间为2～5h。Preferably, the temperature of the calcination is 250-550° C., and the calcination time is 3-6 hours; the temperature of the post-nitriding treatment is 650-800° C., and the time of the post-nitridation treatment is 2-5 hours.
所述的以Ce-MOF为前驱体的二氧化铈/氮化钛纳米管的制备方法，包括如下具体步骤：The preparation method of the ceria/titanium nitride nanotube with Ce-MOF as the precursor comprises the following specific steps:
S1.先将铈源和有机羧酸配体溶解在有机溶剂中，在50～180℃反应1～8h，过滤后于真空烘箱中干燥，得到Ce-MOF前驱框架；S1. Dissolve the cerium source and the organic carboxylic acid ligand in an organic solvent, react at 50-180°C for 1-8 hours, filter and dry in a vacuum oven to obtain the Ce-MOF precursor framework;
S2.将Ce-MOF前驱框架、钛源溶于溶剂中，并加入到带有聚四氟乙烯内衬的高压反应釜中，在110～200℃下进行反应；S2. Dissolve the Ce-MOF precursor framework and titanium source in a solvent, and add them to a high-pressure reactor with a polytetrafluoroethylene liner, and react at 110-200 ° C;
S3.反应结束后冷却、过滤、洗涤、干燥，经过煅烧后得到催化剂前体；S3. cooling, filtering, washing and drying after the reaction is finished, and obtaining a catalyst precursor after calcination;
S4.再将催化剂前体放入管式炉进行后氮化处理，即得到二氧化铈/氮化钛纳米管(CeO2/TiN NTs)。S4. Putting the catalyst precursor into a tube furnace for post-nitridation treatment to obtain ceria/titanium nitride nanotubes (CeO2 /TiN NTs).
优选地，步骤S2中所述反应的时间为7～17h；步骤S3中所述干燥的温度为60～100℃，所述干燥的时间为10～16h。Preferably, the reaction time in step S2 is 7-17 hours; the drying temperature in step S3 is 60-100° C., and the drying time is 10-16 hours.
优选地，步骤S4中所述二氧化铈/氮化钛纳米管中Ce的量为10～40wt％。Preferably, the amount of Ce in the ceria/titanium nitride nanotubes in step S4 is 10-40wt%.
所述的以Ce-MOF为前驱体的二氧化铈/氮化钛纳米管在光催化材料、介电及微波吸收材料、高温微波吸收材料及电极催化剂载体材料和导热材料领域中的应用。The application of the ceria/titanium nitride nanotube with Ce-MOF as precursor in the fields of photocatalytic materials, dielectric and microwave absorbing materials, high temperature microwave absorbing materials, electrode catalyst carrier materials and heat conducting materials.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1.本发明的以Ce-MOF为前驱体的二氧化铈/氮化钛纳米管(CeO2/TiN NTs)具有规整的形貌和较大的比表面积，较高的导电性，同时具有良好的电化学性能。1. The ceria/titanium nitride nanotubes (CeO2 /TiN NTs) with Ce-MOF as the precursor of the present invention have regular morphology and larger specific surface area, higher electrical conductivity, and have good electrochemical performance.
2.本发明的方法所需设备要求简单且操作容易，安全，同时成本低，可以大规模生产。2. The equipment required by the method of the present invention is simple, easy to operate, safe, low in cost, and can be produced on a large scale.
附图说明Description of drawings
图1为实施例3中制备的CeO2/TiN NTs的SEM照片。FIG. 1 is a SEM photo of CeO2 /TiN NTs prepared in Example 3.
图2为实施例3所制备的CeO2/TiN NTs与GC的循环伏安对比图。Fig. 2 is a comparison chart of cyclic voltammetry between CeO2 /TiN NTs prepared in Example 3 and GC.
图3为实施例4中制备的CeO2/TiN NTs的SEM照片。FIG. 3 is a SEM photo of CeO2 /TiN NTs prepared in Example 4. FIG.
图4为实施例5所制备的CeO2/TiN NTs的XRD谱图。FIG. 4 is the XRD spectrum of CeO2 /TiN NTs prepared in Example 5. FIG.
图5为实施例5中制备的CeO2/TiN NTs的SEM照片。FIG. 5 is an SEM photo of CeO2 /TiN NTs prepared in Example 5. FIG.
图6实施例5中制备的CeO2/TiN NTs(a)为氮气吸附脱附曲线，(b)为其对应的BJH的孔径分布图。Fig. 6 CeO2 /TiN NTs prepared in Example 5 (a) is the nitrogen adsorption-desorption curve, (b) is the pore size distribution diagram of the corresponding BJH.
图7为实施例6中制备的CeO2/TiN NTs的SEM照片。FIG. 7 is a SEM photo of CeO2 /TiN NTs prepared in Example 6. FIG.
具体实施方式Detailed ways
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。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。The content of the present invention will be further described below in conjunction with specific examples, but it should not be construed as a limitation of the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
实施例1Example 1
称取醋酸铈0.90g，对苯二甲酸0.75g，溶于50mL甲醇中，混合均匀后加入一个100mL的烧瓶中，然后放入烘箱中，在180℃保温8h，降至室温后取出过滤得到样品。之后将样品在真空干燥箱中干燥16h，即可得到Ce-MOF-1前驱框架。Weigh 0.90g of cerium acetate and 0.75g of terephthalic acid, dissolve them in 50mL of methanol, mix them evenly, add them to a 100mL flask, put them in an oven, keep them warm at 180°C for 8h, and take them out after cooling down to room temperature to obtain a sample . Afterwards, the samples were dried in a vacuum oven for 16 hours to obtain the Ce-MOF-1 precursor framework.
实施例2Example 2
称取醋酸铈1.02g，己二酸0.88g，溶于100mL二丙基甲酰胺中，混合均匀后加入一个100mL的烧瓶中，然后放入烘箱中，在50℃保温8h，降至室温后取出过滤得到样品。之后将样品在真空干燥箱中干燥16h，即可得到Ce-MOF-2前驱框架。Weigh 1.02g of cerium acetate and 0.88g of adipic acid, dissolve them in 100mL of dipropylformamide, mix them evenly, add them to a 100mL flask, put them in an oven, keep them warm at 50°C for 8h, and take them out after cooling down to room temperature The sample was obtained by filtration. Afterwards, the samples were dried in a vacuum oven for 16 hours to obtain the Ce-MOF-2 precursor framework.
实施例3Example 3
1.将称取的2.12gCe-MOF-1前驱框架和25.62g硫酸氧钛依次加入带有聚四氟乙烯内衬(100mL)的高压釜中，再加入20mL丁二醇、20mL丁醚和40mL无水乙醇，将反应物混合均匀。1. Add 2.12g of Ce-MOF-1 precursor framework and 25.62g of titanyl sulfate into an autoclave with a polytetrafluoroethylene liner (100mL) in sequence, then add 20mL of butanediol, 20mL of butyl ether and 40mL of absolute ethanol, and mix the reactants evenly.
2.将上述混合物加入了聚四氟乙烯内衬装进反应釜中，在200℃下反应17h；2. Add the above mixture into a polytetrafluoroethylene liner and put it into the reaction kettle, and react at 200°C for 17h;
3.待反应釜自然冷却到室温，然后过滤，采用乙醇洗涤，再置于60℃烘箱中，干燥时间16h；3. Allow the reaction kettle to cool down to room temperature naturally, then filter, wash with ethanol, and then place it in an oven at 60°C for 16 hours of drying;
4.再置于马弗炉中在250℃煅烧5h，最后在管式炉中800℃煅烧5h，得到CeO2/氮化钛纳米管(CeO2/TiN NTs)。4. Calcined at 250° C. for 5 h in a muffle furnace, and finally calcined at 800° C. for 5 h in a tube furnace to obtain CeO2 /titanium nitride nanotubes (CeO2 /TiN NTs).
图1为本实施例中制备的CeO2/TiN NTs的SEM照片。从图1中可以看出，所得CeO2/TiN NTs平均直径在50～200nm，由Ce-MOF-1和氮化钛纳米管组合而成的CeO2/TiN NTs，得到CeO2/TiN NTs具有规整的形貌。图2为本实施例制备的CeO2/TiN NTs与玻碳电极的循环伏安对比图。测试条件为室温下在0.5mol/L的H2SO4溶液，扫描电位为-0.2～1.0V(vs.Ag/AgCl)，扫描速率50mV/s。从图2中可知，经过50圈扫描后，并无氧化还原峰的存在，表明CeO2/TiN NTs具有良好的电化学性能，且其电化学性能明显高于玻碳电极(GC)。Fig. 1 is a SEM photo of CeO2 /TiN NTs prepared in this example. It can be seen from Figure 1 that the average diameter of the obtained CeO2 /TiN NTs is 50-200 nm, and the CeO2 /TiN NTs composed of Ce-MOF-1 and titanium nitride nanotubes are obtained, and the CeO2 /TiN NTs have regular shape. Fig. 2 is a comparison chart of cyclic voltammetry between CeO2 /TiN NTs and glassy carbon electrodes prepared in this example. The test condition is 0.5mol/L H2 SO4 solution at room temperature, the scanning potential is -0.2～1.0V (vs.Ag/AgCl), and the scanning rate is 50mV/s. It can be seen from Figure 2 that after 50 cycles of scanning, there is no redox peak, indicating that CeO2 /TiN NTs has good electrochemical performance, and its electrochemical performance is significantly higher than that of glassy carbon electrode (GC).
实施例4Example 4
1.将称取的2.12gCe-MOF-1前驱框架和18.82g硫酸氧钛依次加入带有聚四氟乙烯内衬(100mL)的高压釜中，再加入13mL丁二醇、13mL丁醚和26mL无水乙醇，将反应物混合均匀。1. Add 2.12g of Ce-MOF-1 precursor framework and 18.82g of titanyl sulfate into an autoclave with a polytetrafluoroethylene liner (100mL) in sequence, then add 13mL of butanediol, 13mL of butyl ether and 26mL of absolute ethanol, and mix the reactants evenly.
2.将上述混合物加入聚四氟乙烯内衬装进反应釜中，在200℃下反应16h；待反应釜自然冷却到室温，然后过滤，采用乙醇洗涤，再置于100℃烘箱中，干燥时间16h；2. Add the above mixture into a polytetrafluoroethylene liner and put it into a reaction kettle, and react at 200°C for 16 hours; wait for the reaction kettle to cool down to room temperature naturally, then filter, wash with ethanol, and then place it in an oven at 100°C for a drying time of 16h;
3.再置于马弗炉中在300℃煅烧6h，最后在管式炉中800℃煅烧5h，得到基于Ce-MOF的氮化钛纳米管。3. Put it in a muffle furnace for calcination at 300° C. for 6 hours, and finally calcine it in a tube furnace for 5 hours at 800° C. to obtain Ce-MOF-based titanium nitride nanotubes.
图3为本实施例中制备的CeO2/TiN NTs的SEM照片。从图3中可以看出，所得CeO2/TiN NTs的平均直径在50-200nm，由Ce-MOF-1和氮化钛纳米管组合而成的CeO2/TiN NTs。Fig. 3 is a SEM photo of CeO2 /TiN NTs prepared in this example. It can be seen from Figure 3 that the average diameter of the obtained CeO2 /TiN NTs is 50-200 nm, and the CeO2 /TiN NTs are composed of Ce-MOF-1 and titanium nitride nanotubes.
实施例5Example 5
1.将称取的2.12gCe-MOF-2前驱框架和25.62g硫酸氧钛依次加入带有聚四氟乙烯内衬(100mL)的高压釜中，再加入14mL丁二醇、14mL丁醚和28mL无水乙醇，将反应物混合均匀。1. Add 2.12g of Ce-MOF-2 precursor framework and 25.62g of titanyl sulfate into an autoclave with a polytetrafluoroethylene liner (100mL) in sequence, then add 14mL of butanediol, 14mL of butyl ether and 28mL of absolute ethanol, and mix the reactants evenly.
2.把上述混合物加入聚四氟乙烯内衬装进反应釜中，在110℃下反应16h；待反应釜自然冷却到室温，然后过滤，采用乙醇洗涤，再置于100℃烘箱中，干燥时间16h。2. Add the above mixture into a polytetrafluoroethylene liner and put it into a reaction kettle, and react at 110°C for 16 hours; wait for the reaction kettle to cool down to room temperature naturally, then filter, wash with ethanol, and then place it in an oven at 100°C for a drying time of 16h.
4.再置于马弗炉中550℃煅烧5h，最后在管式炉中700℃煅烧5h，得到CeO2/TiNNTs。4. Calcined in a muffle furnace at 550°C for 5 hours, and finally in a tube furnace at 700°C for 5 hours to obtain CeO2 /TiNNTs.
图4为本实施例所制备的CeO2/TiN NTs的XRD图。从图4中可知，CeO2/TiN NTs的特征衍射峰位置分别在36.8°、42.6°、61.9°、74.2°、77.9°出现面心立方结构(fcc)的TiN的特征衍射峰，这表明该方法可以制备纯相面心立方结构(fcc)的TiN。样品在28.8°、33.2°、56.2°、76.2°、80°出现立方形的CeO2的特征衍射峰，这表明该方法可以制备出CeO2/TiNNTs。所得CeO2/TiN NTs的SEM如图5所示，所得CeO2/TiN NTs平均直径在50～200nm，由Ce-MOF-2和氮化钛纳米管组合而成的CeO2/TiN NTs。图6本实施例中制备的CeO2/TiN NTs(a)为氮气吸附脱附曲线，(b)为其对应的BJH的孔径分布图。由图6可知，CeO2/TiN NTs的氮气吸附脱附曲线是带有典型H3滞后环的Ⅳ型等温线，说明CeO2/TiN NTs具有丰富的介孔存在。图6中(b)为BJH孔径分布曲线，可知样品CeO2/TiN NTs存在较多的介孔。此外，通过BET公式计算可得CeO2/TiN NTs的比表面积为148cm2g-1，这主要归因于Ce-MOF具有较大的比表面积。Fig. 4 is an XRD pattern of CeO2 /TiN NTs prepared in this example. It can be seen from Figure 4 that the characteristic diffraction peaks of CeO2 /TiN NTs appear at 36.8°, 42.6°, 61.9°, 74.2°, and 77.9° respectively, and the characteristic diffraction peaks of TiN with face-centered cubic structure (fcc) appear, which indicates that the The method can prepare TiN with pure face-centered cubic structure (fcc). The characteristic diffraction peaks of cubic CeO2 appeared at 28.8°, 33.2°, 56.2°, 76.2°, and 80°, which indicated that CeO2 /TiNNTs could be prepared by this method. The SEM of the obtained CeO2 /TiN NTs is shown in FIG. 5 , the average diameter of the obtained CeO2 /TiN NTs is 50-200 nm, and the CeO2 /TiN NTs are composed of Ce-MOF-2 and titanium nitride nanotubes. Fig. 6 CeO2 /TiN NTs prepared in this example (a) is the nitrogen adsorption-desorption curve, (b) is the pore size distribution diagram of the corresponding BJH. It can be seen from Figure 6 that the nitrogen adsorption-desorption curve of CeO2 /TiN NTs is a type IV isotherm with a typical H3 hysteresis loop, indicating that CeO2 /TiN NTs has abundant mesopores. Figure 6(b) is the BJH pore size distribution curve, which shows that the sample CeO2 /TiN NTs has more mesopores. In addition, the specific surface area of CeO2 /TiN NTs calculated by the BET formula is 148 cm2 g-1 , which is mainly attributed to the large specific surface area of Ce-MOF.
实施例6Example 6
1.将称取2.12gCe-MOF-2前驱框架和18.82g硫酸氧钛依次加入带有聚四氟乙烯内衬(100mL)的高压釜中，再加入20mL丁二醇、20mL丁醚和40mL无水乙醇，将反应物混合均匀。1. Add 2.12g of Ce-MOF-2 precursor framework and 18.82g of titanyl sulfate into an autoclave with Teflon liner (100mL) in sequence, then add 20mL of butanediol, 20mL of butyl ether and 40mL of water, ethanol, and mix the reactants evenly.
2.将上述混合物加入聚四氟乙烯内衬装进反应釜中，在200℃下反应17h；待反应釜自然冷却到室温，然后过滤，采用乙醇洗涤，再置于100℃烘箱中，干燥时间16h。2. Add the above mixture into a polytetrafluoroethylene liner and put it into a reaction kettle, and react at 200°C for 17 hours; wait for the reaction kettle to cool down to room temperature naturally, then filter, wash with ethanol, and then place it in an oven at 100°C for a drying time of 16h.
5.再置于马弗炉中500℃煅烧6h，最后在管式炉中700℃煅烧5h，得到CeO2/TiNNTs。5. Calcined in a muffle furnace at 500°C for 6 hours, and finally in a tube furnace at 700°C for 5 hours to obtain CeO2 /TiNNTs.
所得CeO2/TiN NTs的SEM如图7所示，所得CeO2/TiN NTs的平均直径在50～200nm，Ce-MOF-2和氮化钛纳米管组合而成的CeO2/TiN NTs。The SEM of the obtained CeO2 /TiN NTs is shown in FIG. 7 , the average diameter of the obtained CeO2 /TiN NTs is 50-200 nm, and the CeO2 /TiN NTs are composed of Ce-MOF-2 and titanium nitride nanotubes.
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、组合和简化，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 embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations and modifications made without departing from the spirit and principles of the present invention Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN201810601404.4ACN109012722B (en) | 2018-06-12 | 2018-06-12 | A kind of ceria/titanium nitride nanotube with Ce-MOF as precursor and its preparation method and application |
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| CN201810601404.4ACN109012722B (en) | 2018-06-12 | 2018-06-12 | A kind of ceria/titanium nitride nanotube with Ce-MOF as precursor and its preparation method and application |
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| CN201810601404.4AExpired - Fee RelatedCN109012722B (en) | 2018-06-12 | 2018-06-12 | A kind of ceria/titanium nitride nanotube with Ce-MOF as precursor and its preparation method and application |
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