CN111744519A - A kind of preparation method of three-dimensional MXene-based carrier hydrogen evolution catalyst - Google Patents

A kind of preparation method of three-dimensional MXene-based carrier hydrogen evolution catalyst Download PDF

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CN111744519A
CN111744519A CN202010776730.6A CN202010776730A CN111744519A CN 111744519 A CN111744519 A CN 111744519A CN 202010776730 A CN202010776730 A CN 202010776730A CN 111744519 A CN111744519 A CN 111744519A
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徐晨曦
王冉冉
常周
方中威
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Abstract

The invention discloses a preparation method of a three-dimensional MXene-based catalyst for hydrogen evolution reaction, which utilizes a three-dimensional MXene-based material as a catalyst carrier for the electrolysis water hydrogen evolution reaction under an alkaline condition and loads catalytic active particles so as to prepare the three-dimensional catalyst. Compared with the traditional noble metal catalyst such as (Pt/C) catalyst, the novel catalyst prepared by the invention has better electrocatalytic activity and stability.

Description

一种三维MXene基载体的析氢催化剂的制备方法A kind of preparation method of three-dimensional MXene-based carrier hydrogen evolution catalyst

技术领域technical field

本发明属于电催化技术领域，具体涉及一种三维MXene基载体的析氢催化剂的制备方法。The invention belongs to the technical field of electrocatalysis, and in particular relates to a preparation method of a three-dimensional MXene-based carrier hydrogen evolution catalyst.

背景技术Background technique

电解水制氢是一种清洁高效的制氢技术，其制备条件温和，对设备要求低且制得的氢气纯度可达到99.99％，具有很高的经济效益和社会效益。与其他的制氢方法相比较，电解水制氢利用清洁的水作为反应的原料，制备方式绿色环保，因此被公认为是可持续生产氢气的方法。因此，电解水制氢技术将成为未来制氢工业的核心技术。Hydrogen production by electrolysis of water is a clean and efficient hydrogen production technology. Its preparation conditions are mild, the equipment requirements are low, and the purity of the produced hydrogen can reach 99.99%, which has high economic and social benefits. Compared with other hydrogen production methods, electrolysis of water for hydrogen production uses clean water as the raw material for the reaction, and the preparation method is green and environmentally friendly, so it is recognized as a method for sustainable hydrogen production. Therefore, water electrolysis hydrogen production technology will become the core technology of the future hydrogen production industry.

贵金属材料如铂、钯等是目前催化性能最佳、最符合的析氢催化剂，但由于其地壳储量少，价格昂贵，不能够大规模的应用于工业制氢中。目前，研究工作者正致力于寻找结构更新颖、催化活性更高、电化学性能更稳定的电解水析氢反应催化剂。因此，研究结构稳定、能高效率的催化反应进行的电解水析氢反应催化剂是电解水制氢的重要发展趋势。Precious metal materials such as platinum and palladium are currently the best and most suitable hydrogen evolution catalysts, but due to their low crustal reserves and high prices, they cannot be applied in large-scale industrial hydrogen production. At present, researchers are working to find catalysts for the hydrogen evolution reaction of water electrolysis with novel structures, higher catalytic activity, and more stable electrochemical performance. Therefore, it is an important development trend to study the hydrogen evolution reaction catalyst of electrolysis water with stable structure and high efficiency catalytic reaction.

发明内容SUMMARY OF THE INVENTION

本发明旨在提供一种三维MXene基载体的析氢催化剂的制备方法，通过使用新型的三维MXene基复合载体负载催化剂活性颗粒，合成氢析出催化剂。这种载体具有三维结构，具有大的比表面积和更多的催化剂活性颗粒附着位点，比传统的炭黑做催化剂载体更具有优势。用这种载体制备的催化剂有更高的催化活性、更好的电化学稳定性。The present invention aims to provide a preparation method of a three-dimensional MXene-based carrier hydrogen evolution catalyst. The hydrogen evolution catalyst is synthesized by using a novel three-dimensional MXene-based composite carrier to support catalyst active particles. This carrier has a three-dimensional structure, has a large specific surface area and more attachment sites for catalyst active particles, which is more advantageous than traditional carbon black as a catalyst carrier. The catalyst prepared with this carrier has higher catalytic activity and better electrochemical stability.

本发明三维MXene基载体的析氢催化剂的制备方法，是使用MXene与碳材料复合作为碱性条件下电解水析氢反应的催化剂载体，随后负载催化剂活性颗粒，即可获得新型载体析氢催化剂，以提高其催化活性及稳定性。具体包括如下步骤：The preparation method of the three-dimensional MXene-based carrier hydrogen evolution catalyst of the present invention is to use the composite of MXene and carbon material as a catalyst carrier for the hydrogen evolution reaction of water electrolysis under alkaline conditions, and then load the catalyst active particles to obtain a new carrier hydrogen evolution catalyst, so as to improve its performance. Catalytic activity and stability. Specifically include the following steps:

步骤1：将0.1～20份的MXene加入1～20份的溶剂中，超声分散均匀获得MXene分散液；Step 1: adding 0.1-20 parts of MXene to 1-20 parts of solvent, and ultrasonically dispersing it uniformly to obtain a MXene dispersion;

步骤2：将0.1～20份的碳材料加入1～20份的溶剂中，超声分散均匀获得碳材料分散液；Step 2: adding 0.1-20 parts of carbon material to 1-20 parts of solvent, and ultrasonically dispersing it uniformly to obtain a carbon material dispersion;

步骤3：将步骤1获得的MXene分散液与步骤2获得的碳材料分散液混合并超声分散均匀，转移至水热反应釜中，通入氮气0.5-5小时，随后进行水热反应，反应结束后冷却并洗涤若干次，冷冻干燥12小时，获得MXene-碳材料三维复合载体；Step 3: Mix the MXene dispersion obtained in Step 1 with the carbon material dispersion obtained in Step 2, and ultrasonically disperse it uniformly, transfer it to a hydrothermal reactor, introduce nitrogen for 0.5-5 hours, and then perform a hydrothermal reaction, and the reaction ends After cooling and washing several times, freeze-drying for 12 hours to obtain MXene-carbon material three-dimensional composite carrier;

步骤4：将0.1～40份步骤3获得的MXene-碳材料三维复合载体分散到1～40份溶剂中，超声分散0.1-20小时；Step 4: Disperse 0.1-40 parts of the MXene-carbon material three-dimensional composite carrier obtained in step 3 into 1-40 parts of a solvent, and ultrasonically disperse for 0.1-20 hours;

步骤5：按照催化活性颗粒的质量为催化剂总质量1～60％的比例计算出所需催化剂活性颗粒前驱体的量，在溶剂中超声分散均匀后加入到步骤4获得的分散液中；Step 5: Calculate the amount of catalyst active particle precursor required according to the ratio that the mass of the catalytically active particles is 1 to 60% of the total mass of the catalyst, and then add it to the dispersion obtained in step 4 after ultrasonically dispersing it in a solvent uniformly;

步骤6：向步骤5获得的混合分散液中滴加还原剂溶液，滴加完成后用去离子水洗涤，随后置于真空干燥箱中真空干燥0.5小时以上，即可得到三维MXene基载体的析氢催化剂。Step 6: Add the reducing agent solution dropwise to the mixed dispersion obtained in Step 5, wash with deionized water after the dropwise addition, and then place it in a vacuum drying box for vacuum drying for more than 0.5 hours to obtain the hydrogen evolution of the three-dimensional MXene-based carrier catalyst.

本发明的制备过程中，各原料按质量份数构成如下：In the preparation process of the present invention, each raw material is constituted as follows by mass fraction:

Figure BDA0002618706190000021
Figure BDA0002618706190000021

所述MXene为Ti3C2、Ti2C、Nb3C2、Nb2C、TiNbC、Cr2TiC、Ti3CN、Ti4N3、Ta4C3、V2C、Mo2C或MoTiC2。The MXene is Ti 3 C 2 , Ti 2 C, Nb 3 C 2 , Nb 2 C, TiNbC, Cr 2 TiC, Ti 3 CN, Ti 4 N 3 , Ta 4 C 3 , V 2 C, Mo 2 C or MoTiC 2 .

所述碳材料为氧化石墨烯(GO)、石墨烯、碳纳米管(CNT)或活性炭。The carbon material is graphene oxide (GO), graphene, carbon nanotube (CNT) or activated carbon.

所述催化剂活性颗粒前驱体为H2PtCl6·6H2O、PdCl2、Na2PdCl4、K2PdCl6、NiCl2、CoCl2、CuCl2、ZnCl2中的任一种。The catalyst active particle precursor is any one of H 2 PtCl 6 ·6H 2 O, PdCl 2 , Na 2 PdCl 4 , K 2 PdCl 6 , NiCl 2 , CoCl 2 , CuCl 2 , and ZnCl 2 .

所述还原剂为NaBH4、水合肼、LiBH4、甲醛中的任一种。The reducing agent is any one of NaBH 4 , hydrazine hydrate, LiBH 4 and formaldehyde.

所述溶剂为去离子水、乙二醇中的任一种。上述溶剂的质量份数是指制备过程中使用的溶剂总量。The solvent is any one of deionized water and ethylene glycol. The mass fraction of the above-mentioned solvent refers to the total amount of the solvent used in the preparation process.

进一步地，所述MXene与碳材料的混合溶液中两者的质量比为0.1～10：0.1～10。Further, the mass ratio of the MXene and the carbon material in the mixed solution is 0.1-10:0.1-10.

进一步地，步骤3中，水热反应的反应温度为80～160℃，反应时间为1～10小时。Further, in step 3, the reaction temperature of the hydrothermal reaction is 80-160° C., and the reaction time is 1-10 hours.

进一步地，所述还原剂与催化剂活性颗粒前驱体的质量比为1～20:1。Further, the mass ratio of the reducing agent to the catalyst active particle precursor is 1-20:1.

本发明的有益效果体现在：The beneficial effects of the present invention are embodied in:

本发明通过MXene和碳材料在高温水热下的复合制备具有三维结构的新材料，用作电解水析氢反应催化剂的载体。这种载体具有相互连通的孔洞，是多孔状的三维结构。利用这种新型载体制备出的析氢催化剂，相比于传统的Pt/C催化剂，有着更好的电催化性能和电化学稳定性。The invention prepares a new material with a three-dimensional structure through the composite of MXene and carbon material under high temperature hydrothermal, and is used as a carrier for a catalyst for electrolysis of water and hydrogen evolution reaction. This carrier has interconnected pores and is a porous three-dimensional structure. Compared with the traditional Pt/C catalyst, the hydrogen evolution catalyst prepared by this novel carrier has better electrocatalytic performance and electrochemical stability.

附图说明Description of drawings

图1是Ti3C2Tx-GO三维复合载体的微观形貌图。Figure 1 is a microscopic topography of the Ti 3 C 2 T x -GO three-dimensional composite carrier.

图2是Pt颗粒负载在Ti3C2Tx-GO三维复合载体上获得的催化剂在1M KOH溶液环境下的催化析氢极化曲线。Figure 2 is the polarization curve of the catalytic hydrogen evolution of the catalyst obtained by supporting Pt particles on the Ti 3 C 2 T x -GO three-dimensional composite support in the environment of 1 M KOH solution.

图3是Pt颗粒负载在Ti3C2Tx-GO三维复合载体上获得的催化剂在1M KOH溶液环境下25000s恒电流稳定性测试。Figure 3 shows the galvanostatic stability test of the catalyst obtained by supporting Pt particles on a Ti 3 C 2 T x -GO three-dimensional composite support in a 1 M KOH solution environment for 25000 s.

具体实施方式Detailed ways

为了使本发明的目的、技术方案与优点更加清楚明白，下面结合附图及实施例对本发明进行进一步详细说明。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

实施例1：Example 1:

本实施例中三维MXene基载体的析氢催化剂，原料为：MXene40mg，GO40mg，催化剂活性颗粒前驱体80mg，还原剂240mg，溶剂120mg。The hydrogen evolution catalyst of the three-dimensional MXene-based carrier in this example has raw materials: 40 mg of MXene, 40 mg of GO, 80 mg of catalyst active particle precursor, 240 mg of reducing agent, and 120 mg of solvent.

其中，所述MXene为Ti3C2Tx，所述碳材料为GO，所述催化剂活性颗粒前驱体为H2PtCl6·6H2O，所述还原剂为NaBH4，所述溶剂为去离子水。Wherein, the MXene is Ti 3 C 2 T x , the carbon material is GO, the catalyst active particle precursor is H 2 PtCl 6 ·6H 2 O, the reducing agent is NaBH 4 , and the solvent is Ionized water.

本实施例中三维MXene基载体的析氢催化剂的制备方法，包含如下操作步骤：The preparation method of the hydrogen evolution catalyst of the three-dimensional MXene-based carrier in the present embodiment comprises the following operation steps:

(1)称取40mg的Ti3C2Tx在20mg的去离子水中超声分散30分钟；(1) Weigh 40 mg of Ti 3 C 2 T x and ultrasonically disperse it in 20 mg of deionized water for 30 minutes;

(2)称取40mg的GO在20mg的去离子水中超声分散30分钟；(2) Weigh 40 mg of GO and disperse it in 20 mg of deionized water by ultrasonic for 30 minutes;

(3)将Ti3C2Tx分散液与GO分散液混合，得到的混合分散液在超声机中超声1小时，随后将混合分散液转移至水热反应釜中，通入氮气0.5小时，之后在烘箱中100℃水热反应3小时；(3) Mix the Ti 3 C 2 T x dispersion with the GO dispersion, and sonicate the obtained mixed dispersion in an ultrasonic machine for 1 hour, then transfer the mixed dispersion to a hydrothermal reactor, and pass nitrogen gas for 0.5 hours, After that, the hydrothermal reaction was performed in an oven at 100°C for 3 hours;

(4)水热反应之后的反应物于-60℃冷冻干燥12小时，即得三维Ti3C2Tx基载体；(4) The reactant after the hydrothermal reaction was freeze-dried at -60° C. for 12 hours to obtain a three-dimensional Ti 3 C 2 T x -based carrier;

(5)称取80mg三维Ti3C2Tx基载体分散在80ml去离子水中，超声均匀后加入80mgH2PtCl6·6H2O；(5) Weigh 80 mg of three-dimensional Ti 3 C 2 T x -based carrier and disperse it in 80 ml of deionized water, and add 80 mg of H 2 PtCl 6 ·6H 2 O after ultrasonic uniformity;

(6)加入240mgNaBH4，待气泡完全消失后，用去离子水离心洗涤6次，对洗涤后的样品进行抽滤，将抽滤之后得到的滤饼在真空干燥箱中于60℃烘干12小时，即得三维Ti3C2Tx基载体的Pt/Ti3C2Tx-GO析氢催化剂。(6) Add 240 mg of NaBH 4 , after the bubbles disappear completely, centrifuge and wash 6 times with deionized water, carry out suction filtration on the washed sample, and dry the filter cake obtained after suction filtration at 60° C. in a vacuum drying oven for 12 Within hours, a Pt/Ti 3 C 2 T x -GO hydrogen evolution catalyst with a three-dimensional Ti 3 C 2 T x -based carrier was obtained.

随后，在3ml的离心管中加入450μL去离子水、500μL异丙醇、50μL Nafion膜混合溶液，称取5.0mg催化剂粉末，将其加入到装有上述溶液的离心管中，在超声机中超声来得到分散均匀的电催化剂浆料。Ti3C2Tx与GO在水热反应后形成多孔状的三维结构，两组分相互重叠或聚结导致骨架的物理交联位点的形成。三维Pt/Ti3C2Tx-GO催化剂在10mA cm-2下表现出58mV的过电位，远低于商用Pt/C(86mV)的过电位。并且该三维催化剂在10mA cm-2的恒电流作用下运行25000s后，过电位下降仅为21mV，展现出良好的稳定性。Subsequently, 450 μL of deionized water, 500 μL of isopropanol, and 50 μL of Nafion membrane mixed solution were added to a 3 ml centrifuge tube, and 5.0 mg of catalyst powder was weighed, added to the centrifuge tube containing the above solution, and sonicated in an ultrasonic machine. to obtain a uniformly dispersed electrocatalyst slurry. Ti 3 C 2 T x and GO form a porous three-dimensional structure after hydrothermal reaction, and the two components overlap or coalesce with each other, resulting in the formation of physical cross-linking sites of the framework. The three-dimensional Pt/Ti 3 C 2 T x -GO catalyst exhibits an overpotential of 58 mV at 10 mA cm -2 , which is much lower than that of commercial Pt/C (86 mV). Moreover, after the three-dimensional catalyst was operated under the constant current of 10 mA cm -2 for 25000 s, the overpotential drop was only 21 mV, showing good stability.

实施例2：Example 2:

本实施例中三维MXene基载体的析氢催化剂，原料为：MXene40mg，GO 40mg，催化剂活性颗粒前驱体80mg，还原剂240mg，溶剂120mg。The hydrogen evolution catalyst of the three-dimensional MXene-based carrier in this example, the raw materials are: MXene 40mg, GO 40mg, catalyst active particle precursor 80mg, reducing agent 240mg, solvent 120mg.

其中，所述MXene为Ti3C2Tx，所述碳材料为GO，所述催化剂活性颗粒前驱体为H2PtCl6·6H2O，所述还原剂为NaBH4，所述溶剂为去离子水。Wherein, the MXene is Ti 3 C 2 T x , the carbon material is GO, the catalyst active particle precursor is H 2 PtCl 6 ·6H 2 O, the reducing agent is NaBH 4 , and the solvent is Ionized water.

本实施例中三维MXene基载体的析氢催化剂的制备方法，包含如下操作步骤：The preparation method of the hydrogen evolution catalyst of the three-dimensional MXene-based carrier in the present embodiment comprises the following operation steps:

(1)称取40mg的Ti3C2Tx在20mg的去离子水中超声分散30分钟；(1) Weigh 40 mg of Ti 3 C 2 T x and ultrasonically disperse it in 20 mg of deionized water for 30 minutes;

(2)称取40mg的GO在20mg的去离子水中超声分散30分钟；(2) Weigh 40 mg of GO and disperse it in 20 mg of deionized water by ultrasonic for 30 minutes;

(3)将Ti3C2Tx分散液与GO分散液混合，得到的混合分散液在超声机中超声1小时，随后将混合分散液转移至水热反应釜中，通入氮气0.5小时，之后在烘箱中80℃水热反应4小时；(3) Mix the Ti 3 C 2 T x dispersion with the GO dispersion, and sonicate the obtained mixed dispersion in an ultrasonic machine for 1 hour, then transfer the mixed dispersion to a hydrothermal reactor, and pass nitrogen gas for 0.5 hours, After that, the hydrothermal reaction was performed in an oven at 80°C for 4 hours;

(4)水热反应之后的反应物于-60℃冷冻干燥12小时，即得三维Ti3C2Tx基载体；(4) The reactant after the hydrothermal reaction was freeze-dried at -60° C. for 12 hours to obtain a three-dimensional Ti 3 C 2 T x -based carrier;

(5)称取80mg三维Ti3C2Tx基载体分散在80ml去离子水中，超声均匀后加入80mgH2PtCl6·6H2O；(5) Weigh 80 mg of three-dimensional Ti 3 C 2 T x -based carrier and disperse it in 80 ml of deionized water, and add 80 mg of H 2 PtCl 6 ·6H 2 O after ultrasonic uniformity;

(6)加入240mg NaBH4，待气泡完全消失后，用去离子水离心洗涤6次，对洗涤后的样品进行抽滤，将抽滤之后得到的滤饼在真空干燥箱中于60℃烘干12小时，即得三维Ti3C2Tx基载体的Pt/Ti3C2Tx-GO析氢催化剂。(6) Add 240 mg of NaBH 4 , after the bubbles disappear completely, centrifuge and wash 6 times with deionized water, perform suction filtration on the washed sample, and dry the filter cake obtained after suction filtration at 60° C. in a vacuum drying oven After 12 hours, a three-dimensional Ti 3 C 2 T x -based Pt/Ti 3 C 2 T x -GO hydrogen evolution catalyst was obtained.

随后，在3ml的离心管中加入450μL去离子水、500μL异丙醇、50μL Nafion膜混合溶液，称取5.0mg催化剂粉末，将其加入到装有上述溶液的离心管中，在超声机中超声来得到分散均匀的电催化剂浆料。Ti3C2Tx与GO在水热反应后形成多孔状的三维结构，两组分相互重叠或聚结导致骨架的物理交联位点的形成。三维Pt/Ti3C2Tx-GO催化剂在10mA cm-2下表现出89mV的过电位，展现出良好的电催化性能。Subsequently, 450 μL of deionized water, 500 μL of isopropanol, and 50 μL of Nafion membrane mixed solution were added to a 3 ml centrifuge tube, and 5.0 mg of catalyst powder was weighed and added to the centrifuge tube containing the above solution, and sonicated in an ultrasonic machine. to obtain a uniformly dispersed electrocatalyst slurry. Ti 3 C 2 T x and GO form a porous three-dimensional structure after hydrothermal reaction, and the two components overlap or coalesce with each other, resulting in the formation of physical cross-linking sites of the framework. The three-dimensional Pt/Ti 3 C 2 T x -GO catalyst exhibits an overpotential of 89 mV at 10 mA cm -2 , demonstrating good electrocatalytic performance.

实施例3：Example 3:

本实施例中三维MXene基载体的析氢催化剂，原料为：MXene40mg，GO 40mg，催化剂活性颗粒前驱体80mg，还原剂240mg，溶剂120mg。The hydrogen evolution catalyst of the three-dimensional MXene-based carrier in this example, the raw materials are: MXene 40mg, GO 40mg, catalyst active particle precursor 80mg, reducing agent 240mg, solvent 120mg.

其中，所述MXene为Ti3C2Tx，所述碳材料为GO，所述催化剂活性颗粒前驱体为H2PtCl6·6H2O，所述还原剂为NaBH4，所述溶剂为去离子水。Wherein, the MXene is Ti 3 C 2 T x , the carbon material is GO, the catalyst active particle precursor is H 2 PtCl 6 ·6H 2 O, the reducing agent is NaBH 4 , and the solvent is Ionized water.

本实施例中三维MXene基载体的析氢催化剂的制备方法，包含如下操作步骤：The preparation method of the hydrogen evolution catalyst of the three-dimensional MXene-based carrier in the present embodiment comprises the following operation steps:

(1)称取40mg的Ti3C2Tx在20mg的去离子水中超声分散30分钟；(1) Weigh 40 mg of Ti 3 C 2 T x and ultrasonically disperse it in 20 mg of deionized water for 30 minutes;

(2)称取40mg的GO在20mg的去离子水中超声分散30分钟；(2) Weigh 40 mg of GO and disperse it in 20 mg of deionized water by ultrasonic for 30 minutes;

(3)将Ti3C2Tx分散液与GO分散液混合，得到的混合分散液在超声机中超声1小时，随后将混合分散液转移至水热反应釜中，通入氮气0.5小时，之后在烘箱中100℃水热反应4小时；(3) Mix the Ti 3 C 2 T x dispersion with the GO dispersion, and sonicate the obtained mixed dispersion in an ultrasonic machine for 1 hour, then transfer the mixed dispersion to a hydrothermal reactor, and pass nitrogen gas for 0.5 hours, After that, the hydrothermal reaction was performed in an oven at 100°C for 4 hours;

(4)水热反应之后的反应物于-60℃冷冻干燥12小时，即得三维Ti3C2Tx基载体；(4) The reactant after the hydrothermal reaction was freeze-dried at -60° C. for 12 hours to obtain a three-dimensional Ti 3 C 2 T x -based carrier;

(5)称取80mg三维Ti3C2Tx基载体分散在80ml去离子水中，超声均匀后加入80mgH2PtCl6·6H2O；(5) Weigh 80 mg of three-dimensional Ti 3 C 2 T x -based carrier and disperse it in 80 ml of deionized water, and add 80 mg of H 2 PtCl 6 ·6H 2 O after ultrasonic uniformity;

(6)加入240mg NaBH4，待气泡完全消失后，用去离子水离心洗涤6次，对洗涤后的样品进行抽滤，将抽滤之后得到的滤饼在真空干燥箱中于60℃烘干12小时，即得三维Ti3C2Tx基载体的Pt/Ti3C2Tx-GO析氢催化剂。(6) Add 240 mg of NaBH 4 , after the bubbles disappear completely, centrifuge and wash 6 times with deionized water, perform suction filtration on the washed sample, and dry the filter cake obtained after suction filtration at 60° C. in a vacuum drying oven After 12 hours, a three-dimensional Ti 3 C 2 T x -based Pt/Ti 3 C 2 T x -GO hydrogen evolution catalyst was obtained.

随后，在3ml的离心管中加入450μL去离子水、500μL异丙醇、50μL Nafion膜混合溶液，称取5.0mg催化剂粉末，将其加入到装有上述溶液的离心管中，在超声机中超声来得到分散均匀的电催化剂浆料。Ti3C2Tx与GO在水热反应后形成多孔状的三维结构，两组分相互重叠或聚结导致骨架的物理交联位点的形成。三维Pt/Ti3C2Tx-GO催化剂在10mA cm-2下表现出74mV的过电位，展现出良好的电催化性能。Subsequently, 450 μL of deionized water, 500 μL of isopropanol, and 50 μL of Nafion membrane mixed solution were added to a 3 ml centrifuge tube, and 5.0 mg of catalyst powder was weighed and added to the centrifuge tube containing the above solution, and sonicated in an ultrasonic machine. to obtain a uniformly dispersed electrocatalyst slurry. Ti 3 C 2 T x and GO form a porous three-dimensional structure after hydrothermal reaction, and the two components overlap or coalesce with each other, resulting in the formation of physical cross-linking sites of the framework. The three-dimensional Pt/Ti 3 C 2 T x -GO catalyst exhibits an overpotential of 74 mV at 10 mA cm -2 , demonstrating good electrocatalytic performance.

Claims (10)

1.一种三维MXene基载体的析氢催化剂的制备方法，其特征在于包括以下步骤：1. the preparation method of the hydrogen evolution catalyst of a three-dimensional MXene-based carrier, is characterized in that comprising the following steps: 步骤1：将MXene加入溶剂中，超声分散均匀获得MXene分散液；Step 1: Add MXene to the solvent, and ultrasonically disperse it uniformly to obtain a MXene dispersion; 步骤2：将碳材料加入溶剂中，超声分散均匀获得碳材料分散液；Step 2: adding the carbon material to the solvent, and ultrasonically dispersing it uniformly to obtain a carbon material dispersion; 步骤3：将步骤1获得的MXene分散液与步骤2获得的碳材料分散液混合并超声分散均匀，转移至水热反应釜中，通入氮气0.5-5小时，随后进行水热反应，反应结束后冷却并洗涤若干次，冷冻干燥12小时，获得MXene-碳材料三维复合载体；Step 3: Mix the MXene dispersion obtained in Step 1 with the carbon material dispersion obtained in Step 2, and ultrasonically disperse it uniformly, transfer it to a hydrothermal reactor, introduce nitrogen for 0.5-5 hours, and then perform a hydrothermal reaction, and the reaction ends After cooling and washing several times, freeze-drying for 12 hours to obtain MXene-carbon material three-dimensional composite carrier; 步骤4：将步骤3获得的MXene-碳材料三维复合载体分散到溶剂中，超声分散0.1-20小时；Step 4: Disperse the MXene-carbon material three-dimensional composite carrier obtained in Step 3 into a solvent, and ultrasonically disperse for 0.1-20 hours; 步骤5：按照催化活性颗粒的质量为催化剂总质量1～60％的比例计算出所需催化剂活性颗粒前驱体的量，在溶剂中超声分散均匀后加入到步骤4获得的分散液中；Step 5: Calculate the amount of catalyst active particle precursor required according to the ratio that the mass of the catalytically active particles is 1 to 60% of the total mass of the catalyst, and then add it to the dispersion obtained in step 4 after ultrasonically dispersing it in a solvent uniformly; 步骤6：向步骤5获得的混合分散液中滴加还原剂溶液，滴加完成后用去离子水洗涤，随后置于真空干燥箱中真空干燥0.5小时以上，即可得到三维MXene基载体的析氢催化剂。Step 6: Add the reducing agent solution dropwise to the mixed dispersion obtained in Step 5, wash with deionized water after the dropwise addition, and then place it in a vacuum drying box for vacuum drying for more than 0.5 hours to obtain the hydrogen evolution of the three-dimensional MXene-based carrier catalyst. 2.根据权利要求1所述的制备方法，其特征在于各原料按质量份数构成如下：2. preparation method according to claim 1 is characterized in that each raw material is constituted as follows by mass fraction:
Figure FDA0002618706180000011
Figure FDA0002618706180000011
 3.根据权利要求1或2所述的制备方法，其特征在于：3. preparation method according to claim 1 and 2 is characterized in that: 所述MXene为Ti3C2、Ti2C、Nb3C2、Nb2C、TiNbC、Cr2TiC、Ti3CN、Ti4N3、Ta4C3、V2C、Mo2C或MoTiC2。The MXene is Ti 3 C 2 , Ti 2 C, Nb 3 C 2 , Nb 2 C, TiNbC, Cr 2 TiC, Ti 3 CN, Ti 4 N 3 , Ta 4 C 3 , V 2 C, Mo 2 C or MoTiC 2 . 4.根据权利要求1或2所述的制备方法，其特征在于：4. preparation method according to claim 1 and 2 is characterized in that: 所述碳材料为氧化石墨烯、石墨烯、碳纳米管或活性炭。The carbon material is graphene oxide, graphene, carbon nanotubes or activated carbon. 5.根据权利要求1或2所述的制备方法，其特征在于：5. preparation method according to claim 1 and 2 is characterized in that: 所述催化剂活性颗粒前驱体为H2PtCl6·6H2O、PdCl2、Na2PdCl4、K2PdCl6、NiCl2、CoCl2、CuCl2、ZnCl2中的任一种。The catalyst active particle precursor is any one of H 2 PtCl 6 ·6H 2 O, PdCl 2 , Na 2 PdCl 4 , K 2 PdCl 6 , NiCl 2 , CoCl 2 , CuCl 2 , and ZnCl 2 . 6.根据权利要求1或2所述的制备方法，其特征在于：6. preparation method according to claim 1 and 2 is characterized in that: 所述还原剂为NaBH4、水合肼、LiBH4、甲醛中的任一种。The reducing agent is any one of NaBH 4 , hydrazine hydrate, LiBH 4 and formaldehyde. 7.根据权利要求1或2所述的制备方法，其特征在于：7. preparation method according to claim 1 and 2 is characterized in that: 所述溶剂为去离子水、乙二醇中的任一种。The solvent is any one of deionized water and ethylene glycol. 8.根据权利要求1或2所述的制备方法，其特征在于：8. preparation method according to claim 1 and 2 is characterized in that: 所述MXene与碳材料的混合溶液中两者的质量比为0.1～10：0.1～10。The mass ratio of the MXene and the carbon material in the mixed solution is 0.1-10:0.1-10. 9.根据权利要求1所述的制备方法，其特征在于：9. preparation method according to claim 1, is characterized in that: 步骤3中，水热反应的反应温度为80～160℃，反应时间为1～10小时。In step 3, the reaction temperature of the hydrothermal reaction is 80-160° C., and the reaction time is 1-10 hours. 10.根据权利要求1或2所述的制备方法，其特征在于：10. preparation method according to claim 1 and 2, is characterized in that: 所述还原剂与催化剂活性颗粒前驱体的质量比为1～20:1。The mass ratio of the reducing agent to the catalyst active particle precursor is 1-20:1.
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112310417A (en) * 2020-11-05 2021-02-02 中国科学院合肥物质科学研究院 Preparation method, product and application of three-dimensional platinum/Mxene-reduced graphene oxide catalyst
CN112619679A (en) * 2020-12-15 2021-04-09 河南理工大学 Thorn-ball-shaped Mo2C/CdS photocatalyst, preparation method thereof and photocatalytic method
CN112795937A (en) * 2020-12-24 2021-05-14 郑州大学 Composite material for photoelectrochemical water splitting, preparation method, application and electrode thereof
CN113422077A (en) * 2021-06-22 2021-09-21 合肥工业大学 CO-resistant MXene-based catalyst for proton exchange membrane fuel cell and preparation method thereof
CN113629265A (en) * 2021-08-09 2021-11-09 合肥工业大学 A kind of preparation method of MXene-based anode anti-reverse electrode catalyst for proton exchange membrane fuel cell
CN113718281A (en) * 2021-09-26 2021-11-30 河海大学 Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof
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CN114457371A (en) * 2021-11-05 2022-05-10 天津师范大学 MXene loaded Ni nano-particle composite hydrogen evolution electrocatalyst and preparation method and application thereof
CN114899432A (en) * 2022-05-11 2022-08-12 黑龙江哈船碳材料科技有限公司 Composite electrode material for direct sodium borohydride fuel cell and preparation method thereof
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106981667A (en) * 2017-05-09 2017-07-25 河海大学 A kind of preparation method of two-dimentional titanium carbide/carbon nanotube loaded platinum grain composite
US20170263943A1 (en) * 2016-03-12 2017-09-14 University Of Wyoming Methods, Catalysts, and Supports for Electrochemical Devices
CN108855166A (en) * 2018-06-20 2018-11-23 郑州轻工业学院 A kind of loaded catalyst and preparation method thereof, application
CN109671576A (en) * 2018-12-12 2019-04-23 福建翔丰华新能源材料有限公司 Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof
CN110336045A (en) * 2019-07-12 2019-10-15 合肥工业大学 Preparation method of proton exchange membrane fuel cell cathode catalyst based on MXene/rGO composite carrier
CN110492116A (en) * 2019-08-23 2019-11-22 合肥工业大学 A kind of preparation method of the fuel battery cathod catalyst based on MXene- carbon material complex carrier
CN110876954A (en) * 2019-12-06 2020-03-13 东莞理工学院 A foamed MXene/C3N4/metal composite electrocatalyst and preparation method thereof
EP3680962A1 (en) * 2019-01-09 2020-07-15 The Provost, Fellows, Scholars and other Members of Board of Trinity College Dublin High capacity electrodes enabled by 2d materials in a viscous aqueous ink
CN111468121A (en) * 2020-06-11 2020-07-31 北京林业大学 Preparation and application of an MXene-modified biomass carbon nano-metal catalyst

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170263943A1 (en) * 2016-03-12 2017-09-14 University Of Wyoming Methods, Catalysts, and Supports for Electrochemical Devices
CN106981667A (en) * 2017-05-09 2017-07-25 河海大学 A kind of preparation method of two-dimentional titanium carbide/carbon nanotube loaded platinum grain composite
CN108855166A (en) * 2018-06-20 2018-11-23 郑州轻工业学院 A kind of loaded catalyst and preparation method thereof, application
CN109671576A (en) * 2018-12-12 2019-04-23 福建翔丰华新能源材料有限公司 Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof
EP3680962A1 (en) * 2019-01-09 2020-07-15 The Provost, Fellows, Scholars and other Members of Board of Trinity College Dublin High capacity electrodes enabled by 2d materials in a viscous aqueous ink
CN110336045A (en) * 2019-07-12 2019-10-15 合肥工业大学 Preparation method of proton exchange membrane fuel cell cathode catalyst based on MXene/rGO composite carrier
CN110492116A (en) * 2019-08-23 2019-11-22 合肥工业大学 A kind of preparation method of the fuel battery cathod catalyst based on MXene- carbon material complex carrier
CN110876954A (en) * 2019-12-06 2020-03-13 东莞理工学院 A foamed MXene/C3N4/metal composite electrocatalyst and preparation method thereof
CN111468121A (en) * 2020-06-11 2020-07-31 北京林业大学 Preparation and application of an MXene-modified biomass carbon nano-metal catalyst

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHENXI XU ET.AL: "MXene (Ti3C2Tx) and Carbon Nanotube Hybrid-Supported Platinum Catalysts for the High-Performance Oxygen Reduction Reaction in PEMFC", 《ACS APPLIED MATERIALS & INTERFACES》 *
CONG CUI ET.AL: "Ultrastable MXene@Pt/SWCNTs’ Nanocatalysts for Hydrogen Evolution Reaction", 《ADVANCED FUNCTIONAL MATERIALS》 *
CUIZHEN YANG ET.AL: "Ultrafine Pt Nanoparticle-Decorated 3D Hybrid Architectures Built from Reduced Graphene Oxide and MXene Nanosheets for Methanol Oxidation", 《CHEMISTRY OF MATERIALS》 *
JAROSLAV FILIP ET.AL: "Tailoring Electrocatalytic Properties of Pt Nanoparticles Grown on Ti3C2Tx MXene Surface", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 *
PENG ZHANG ET.AL: "The High-Performance Bifunctional Catalyst Pd/Ti3C2Tx-Carbon Nanotube for Oxygen Reduction and Hydrogen Evolution Reaction in Alkaline Medium", 《ENERGY TECHNOLOGY》 *

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Application publication date: 20201009