CN111359636A - A kind of Mo-S/NF hydrogen evolution material and its preparation method and application - Google Patents

A kind of Mo-S/NF hydrogen evolution material and its preparation method and application Download PDF

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CN111359636A
CN111359636A CN202010151960.3A CN202010151960A CN111359636A CN 111359636 A CN111359636 A CN 111359636A CN 202010151960 A CN202010151960 A CN 202010151960A CN 111359636 A CN111359636 A CN 111359636A
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hydrogen evolution
evolution material
hydrogen
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glassy carbon
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蒋继波
丛海山
陈宇凯
孔玥
唐家斌
胡晓敏
王露露
李学剑
韩生
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Shanghai Institute of Technology
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Abstract

The invention relates to a Mo-S/NF hydrogen evolution material and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) mixing ammonium tetrathiomolybdate and thiourea with water, and performing ultrasonic dispersion to obtain a mixed solution; 2) adding the mixed solution into a reaction kettle, adding foamed nickel serving as a carrier into the reaction kettle, and performing hydrothermal reaction to obtain Mo-S/NF; 3) and calcining the Mo-S/NF under an anaerobic condition to obtain the Mo-S/NF hydrogen evolution material, wherein the hydrogen evolution material is applied to an electro-catalytic hydrogen evolution reaction. Compared with the prior art, the Mo-S/NF hydrogen evolution material prepared by the invention has the advantages of low raw material cost, simple preparation method and good hydrogen evolution effect in alkaline solution, and is expected to be oriented to industrial development.

Description

一种Mo-S/NF析氢材料及其制备方法与应用A kind of Mo-S/NF hydrogen evolution material and its preparation method and application

技术领域technical field

本发明属于氢能源技术领域，涉及一种Mo-S/NF析氢材料及其制备方法与应用。The invention belongs to the technical field of hydrogen energy, and relates to a Mo-S/NF hydrogen evolution material and a preparation method and application thereof.

背景技术Background technique

随着化石燃料日益枯竭，各种新能源被不断开发利用。氢能作为一种可再生的二次能源，其来源广、热值高、清洁、燃烧稳定性好，是继化石燃料等非可再生能源之后新一代被广泛采用的能源载体。碱性电解水制氢是通向氢经济最有潜力的技术手段，但因电解过程中析氢、析氧过电位的存在使反应耗能较大。为了降低能耗，开发低成本且具有高催化活性的阴极电极材料具有重要的意义。泡沫镍是一种商业化的三维开孔、孔隙与金属骨架相互连通的金属功能材料，多应用于镍氢电池电极材料、燃料电池等领域。显然，这类材料具有大的电化学反应界面，在电化学电极材料方面具有较大的应用前景。然而，由于泡沫镍材料在酸性溶液中易发生反应，使其在酸溶液中性能不足。With the depletion of fossil fuels, various new energy sources are continuously developed and utilized. As a renewable secondary energy source, hydrogen energy has a wide range of sources, high calorific value, cleanness and good combustion stability. It is a new generation of widely used energy carriers after non-renewable energy sources such as fossil fuels. Alkaline electrolysis of water for hydrogen production is the most potential technical means leading to the hydrogen economy, but the reaction consumes a lot of energy due to the existence of hydrogen evolution and oxygen evolution overpotentials during the electrolysis process. In order to reduce energy consumption, it is of great significance to develop cathode electrode materials with low cost and high catalytic activity. Nickel foam is a commercialized metal functional material with three-dimensional openings, pores and metal skeleton interconnected, and is mostly used in nickel-metal hydride battery electrode materials, fuel cells and other fields. Obviously, this type of material has a large electrochemical reaction interface and has great application prospects in electrochemical electrode materials. However, because the nickel foam material is easy to react in acid solution, its performance in acid solution is insufficient.

发明内容SUMMARY OF THE INVENTION

本发明的目的就是为了克服上述现有技术存在的催化析氢问题，而提供一种Mo-S/NF析氢材料及其制备方法，以及在电催化析氢方面的应用。该Mo-S/NF析氢材料作为合金催化剂，比多数催化剂合成成本更低，主要元素的地球储备量都比较充足。金属钼中，3d轨道为半充满状态，对氢原子有强烈的吸附作用，与泡沫镍结合后，使泡沫镍的析氢性能大大增强，提高了电化学性能且合成方法简单。The purpose of the present invention is to overcome the problem of catalytic hydrogen evolution in the prior art, and provide a Mo-S/NF hydrogen evolution material and its preparation method, as well as its application in electrocatalytic hydrogen evolution. As an alloy catalyst, the Mo-S/NF hydrogen evolution material has a lower synthesis cost than most catalysts, and the earth reserves of the main elements are relatively sufficient. In the metal molybdenum, the 3d orbital is in a semi-filled state, which has a strong adsorption effect on hydrogen atoms. After combining with the foamed nickel, the hydrogen evolution performance of the foamed nickel is greatly enhanced, the electrochemical performance is improved, and the synthesis method is simple.

本发明的目的可以通过以下技术方案来实现：The object of the present invention can be realized through the following technical solutions:

一种Mo-S/NF析氢材料的制备方法，该方法包括以下步骤：A preparation method of Mo-S/NF hydrogen evolution material, the method comprises the following steps:

1)将四硫代钼酸铵、硫脲与水混合，并进行超声分散，得到混合溶液；1) ammonium tetrathiomolybdate, thiourea and water are mixed, and ultrasonic dispersion is carried out to obtain a mixed solution;

2)将混合溶液加入至反应釜中，并在反应釜中放入泡沫镍(NF)作为载体，经水热反应后得到Mo-S/NF；2) adding the mixed solution into the reactor, and putting nickel foam (NF) into the reactor as a carrier, and obtaining Mo-S/NF after the hydrothermal reaction;

3)将Mo-S/NF在无氧条件下进行煅烧，即得到所述的Mo-S/NF析氢材料。3) calcining the Mo-S/NF under an oxygen-free condition to obtain the Mo-S/NF hydrogen evolution material.

进一步地，步骤1)中，所述的四硫代钼酸铵与硫脲的摩尔比为1:(1-5)，所述的四硫代钼酸铵的摩尔量与水的体积之比为1mmol:(15-25)mL。Further, in step 1), the mol ratio of described ammonium tetrathiomolybdate and thiourea is 1:(1-5), and the ratio of the molar amount of described ammonium tetrathiomolybdate to the volume of water 1 mmol: (15-25) mL.

进一步地，步骤1)中，所述的超声分散的时间为5-10min，超声分散后得到澄清的混合溶液。Further, in step 1), the ultrasonic dispersion time is 5-10min, and a clear mixed solution is obtained after ultrasonic dispersion.

进一步地，步骤2)中，所述的水热反应中，温度为150-200℃，时间为10-15h。Further, in step 2), in the hydrothermal reaction, the temperature is 150-200° C. and the time is 10-15 h.

进一步地，步骤3)中，所述的煅烧在电阻炉中进行，煅烧过程中通入氮气。Further, in step 3), the calcination is carried out in a resistance furnace, and nitrogen gas is introduced into the calcination process.

进一步地，步骤3)中，所述的煅烧中，温度为300-500℃，时间为2-4h。Further, in step 3), in the calcination, the temperature is 300-500°C, and the time is 2-4h.

一种Mo-S/NF析氢材料，该析氢材料采用所述的方法制备而成。A Mo-S/NF hydrogen evolution material prepared by the method.

进一步地，所述的析氢材料中，Mo在泡沫镍中的负载量为15％-20％。Further, in the hydrogen evolution material, the loading of Mo in the nickel foam is 15%-20%.

一种Mo-S/NF析氢材料在电催化析氢反应中的应用。Application of a Mo-S/NF hydrogen evolution material in electrocatalytic hydrogen evolution reaction.

进一步地，在应用时，将所述的Mo-S/NF析氢材料与Nafion溶液混合均匀后，滴涂于玻碳电极上，干燥后得到析氢玻碳电极，作为电催化析氢反应中的工作电极。Further, in application, the Mo-S/NF hydrogen evolution material and Nafion solution are mixed uniformly, then drop-coated on the glassy carbon electrode, and dried to obtain a hydrogen evolution glassy carbon electrode, which is used as a working electrode in the electrocatalytic hydrogen evolution reaction. .

应用方法具体包括如下步骤：The application method specifically includes the following steps:

(1)称取1mg Mo-S/NF析氢材料溶解在100μL配制好的0.5wt％的Nation溶液中，超声下均匀分散半个小时后，吸取12-18μL溶液于玻碳电极上，自然晾干，得到析氢玻碳电极；(1) Weigh 1 mg of Mo-S/NF hydrogen evolution material and dissolve it in 100 μL of prepared 0.5wt% Nation solution. After homogeneously dispersing under ultrasonic for half an hour, draw 12-18 μL of the solution on the glassy carbon electrode and let it dry naturally. , to obtain a glassy carbon electrode for hydrogen evolution;

(2)配制1.0M的氢氧化钾溶液作为电催化的电解液，通入氮气赶跑空气，用1.0M的氢氧化钾溶液清洗得到析氢玻碳电极的表面，接着将得到析氢玻碳电极、Ag/AgCl电极、铂电极接上电化学工作站，在电解液中进行电催化析氢反应。(2) prepare the potassium hydroxide solution of 1.0M as the electrolyte of electrocatalysis, feed nitrogen to drive away the air, clean the surface of the hydrogen-evolution glassy carbon electrode with the potassium hydroxide solution of 1.0M, and then obtain the hydrogen-evolution glassy carbon electrode, The Ag/AgCl electrode and the platinum electrode are connected to the electrochemical workstation, and the electrocatalytic hydrogen evolution reaction is carried out in the electrolyte.

本发明中，水热反应的目的是：高温高压环境促进了反应的进行，得到的产物均匀、无团聚、晶型好，可以更好地负载在泡沫镍上。煅烧的目的是：在高温且氮气保护下，煅烧可以有效地将泡沫镍上其他的元素去除，得到Mo-S/NF析氢材料。In the present invention, the purpose of the hydrothermal reaction is: the high temperature and high pressure environment promotes the reaction, and the obtained product is uniform, free of agglomeration, and has a good crystal form, which can be better supported on the foamed nickel. The purpose of calcination is: under high temperature and nitrogen protection, calcination can effectively remove other elements on the nickel foam to obtain Mo-S/NF hydrogen evolution material.

与现有技术相比，本发明具有以下特点：Compared with the prior art, the present invention has the following characteristics:

1)本发明中，泡沫镍是一种具有三维全贯通网孔结构性能优良的吸声“多孔金属”，泡沫镍的孔率大约为95％，水或气体能够畅通无阻的穿过，镍骨架中空并以冶金状态彼此交连，具有稳定性好、高孔隙率、抗热冲击、体密度小和比表面积大等优点；钼的3d轨道为半充满状态，对氢原子有强烈的吸附作用，与泡沫镍结合后，使泡沫镍的析氢性能大大提高。因此，可以通过引入轨道未充满的金属与泡沫镍结合，使之有利于电极表面吸附氢原子的脱附，从而提高金属镍电极的析氢性能；1) In the present invention, the nickel foam is a sound-absorbing "porous metal" with excellent three-dimensional full-penetrating mesh structure. The porosity of the nickel foam is about 95%, and water or gas can pass through unimpeded. It is hollow and interconnected in a metallurgical state, and has the advantages of good stability, high porosity, thermal shock resistance, low bulk density and large specific surface area; the 3d orbital of molybdenum is half-filled, which has a strong adsorption effect on hydrogen atoms. After being combined with foamed nickel, the hydrogen evolution performance of foamed nickel is greatly improved. Therefore, the hydrogen evolution performance of the metal nickel electrode can be improved by introducing the metal that is not filled with the orbital to combine with the nickel foam, which is beneficial to the desorption of the hydrogen atoms adsorbed on the electrode surface;

2)本发明制备Mo-S/NF析氢材料的原料成本低，制备方式简单，析氢材料的Tafel斜率和过电位低，故析氢效果良好，而且非贵金属元素的引入使材料具有良好的稳定性。2) The present invention has low cost of raw materials for preparing Mo-S/NF hydrogen evolution material, simple preparation method, low Tafel slope and overpotential of hydrogen evolution material, so hydrogen evolution effect is good, and the introduction of non-precious metal elements makes the material have good stability.

3)本发明制备Mo-S/NF析氢材料在碱性介质中电解水，其析氢效果好，而且成本较低。3) The Mo-S/NF hydrogen evolution material prepared by the present invention electrolyzes water in an alkaline medium, and the hydrogen evolution effect is good and the cost is low.

附图说明Description of drawings

图1为实施例1得到的Mo-S/NF析氢材料的Tafel斜率图；Fig. 1 is the Tafel slope diagram of the Mo-S/NF hydrogen evolution material obtained in Example 1;

图2为实施例1得到的Mo-S/NF析氢材料的极化曲线图。FIG. 2 is a polarization curve diagram of the Mo-S/NF hydrogen evolution material obtained in Example 1. FIG.

具体实施方式Detailed ways

下面结合附图和具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. This embodiment is implemented on the premise of the technical solution of the present invention, and provides a detailed implementation manner and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

本发明各实施例中所用的各种原料，如无特殊说明，均为市售。Various raw materials used in each embodiment of the present invention are commercially available unless otherwise specified.

实施例1：Example 1:

四硫代钼酸铵0.5mmolAmmonium tetrathiomolybdate 0.5mmol

硫脲0.5mmolThiourea 0.5mmol

去离子水10mLDeionized water 10mL

析氢材料通过如下步骤的制备方法制备：The hydrogen evolution material is prepared by the preparation method of the following steps:

将0.5mmol四硫代钼酸铵、0.5mmol硫脲溶于10mL去离子水中，在超声震荡仪中超声5min至搅拌溶解。见溶液中无固体颗粒后，转移至高压反应釜，放入8mm×8mm×1mm的泡沫镍，180℃下水热12h。取出Mo-S/NF经处理后放入电阻炉中，通入氮气，在300℃的温度下煅烧2h，最终得到Mo-S/NF析氢材料。Dissolve 0.5 mmol of ammonium tetrathiomolybdate and 0.5 mmol of thiourea in 10 mL of deionized water, and sonicate in an ultrasonic oscillator for 5 min until stirring to dissolve. After seeing that there are no solid particles in the solution, transfer it to a high-pressure reactor, put 8mm×8mm×1mm nickel foam, and heat it with water at 180°C for 12h. The Mo-S/NF was taken out and put into a resistance furnace after treatment, and nitrogen gas was introduced, and it was calcined at a temperature of 300 ℃ for 2 hours, and finally the Mo-S/NF hydrogen evolution material was obtained.

应用实施例1：Application Example 1:

将实施例1的Mo-S/NF析氢材料进行研磨，将玻碳电极表面使用0.05μm的氧化铝研磨干净，除去残留样品，使用乙醇和去离子水冲洗干净，晾干。The Mo-S/NF hydrogen evolution material of Example 1 was ground, and the surface of the glassy carbon electrode was ground with 0.05 μm alumina to remove residual samples, rinsed with ethanol and deionized water, and dried.

(1)用无水甲醇配Nation溶液0.5wt％。称取1mg Mo-S/NF析氢材料溶解在100μL配制好的Nation溶液中，在超声下均匀分散2h。然后再将该溶液吸取12μL于玻碳电极上，自然晾干。(1) Prepare 0.5wt% Nation solution with anhydrous methanol. Weigh 1 mg of Mo-S/NF hydrogen evolution material, dissolve it in 100 μL of prepared Nation solution, and disperse it uniformly under ultrasound for 2 h. Then pipette 12 μL of the solution onto the glassy carbon electrode and dry it naturally.

(2)配制1.0M的氢氧化钾溶液作为电催化的电解液，通入氮气赶跑空气，用1.0M的氢氧化钾溶液清洗析氢玻碳电极的电极表面，接着将析氢玻碳电极、Ag/AgCl电极、铂电极接上电化学工作站，在电解液中测得该电极材料电催化析氢的性能。如图1、图2所示，该材料Tafel斜率为137mV dec-1，在电流密度为10mA cm-2的过电位为343mV。且在经过1000圈CV测试后的LSV曲线和CV测试之前的LSV曲线偏差不大，说明该材料拥有良好的稳定性。(2) prepare a 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introduce nitrogen to drive off the air, clean the electrode surface of the hydrogen-evolution glassy carbon electrode with a 1.0M potassium hydroxide solution, and then combine the hydrogen-evolving glassy carbon electrode, Ag /AgCl electrode and platinum electrode were connected to an electrochemical workstation, and the electrocatalytic hydrogen evolution performance of the electrode material was measured in the electrolyte. As shown in Figure 1 and Figure 2, the Tafel slope of the material is 137mV dec -1 , and the overpotential is 343mV at a current density of 10mA cm -2 . And the LSV curve after 1000 cycles of CV test has little deviation from the LSV curve before CV test, indicating that the material has good stability.

实施例2：Example 2:

四硫代钼酸铵0.5mmolAmmonium tetrathiomolybdate 0.5mmol

硫脲1.0mmolThiourea 1.0mmol

去离子水10mLDeionized water 10mL

析氢材料通过如下步骤的制备方法制备：The hydrogen evolution material is prepared by the preparation method of the following steps:

将0.5mmol四硫代钼酸铵、1.0mmol硫脲溶于10mL去离子水中，在超声震荡仪中超声5min至搅拌溶解。见溶液中无固体颗粒后，转移至高压反应釜，放入8mm×8mm×1mm的泡沫镍，180℃下水热12h。取出Mo-S/NF经处理后放入电阻炉中，通入氮气，在400℃的温度下煅烧2h，最终得到Mo-S/NF析氢材料。Dissolve 0.5 mmol of ammonium tetrathiomolybdate and 1.0 mmol of thiourea in 10 mL of deionized water, and sonicate in an ultrasonic oscillator for 5 min until stirring to dissolve. After seeing that there are no solid particles in the solution, transfer it to a high-pressure reactor, put 8mm×8mm×1mm nickel foam, and heat it with water at 180°C for 12h. The Mo-S/NF was taken out and put into a resistance furnace after treatment. Nitrogen was introduced, and it was calcined at a temperature of 400 °C for 2 h to finally obtain a Mo-S/NF hydrogen evolution material.

应用实施例2：Application Example 2:

将实施例2的Mo-S/NF析氢材料进行研磨，将玻碳电极表面使用0.05μm的氧化铝研磨干净，除去残留样品，使用乙醇和去离子水冲洗干净，晾干。The Mo-S/NF hydrogen evolution material of Example 2 was ground, and the surface of the glassy carbon electrode was ground with 0.05 μm alumina to remove residual samples, rinsed with ethanol and deionized water, and dried.

(1)用无水甲醇配Nation溶液0.5wt％。称取1mg Mo-S/NF析氢材料溶解在100μL配制好的Nation溶液中，在超声下均匀分散2h。然后再将该溶液吸取18μL于玻碳电极上，自然晾干。(1) Prepare 0.5wt% Nation solution with anhydrous methanol. Weigh 1 mg of Mo-S/NF hydrogen evolution material, dissolve it in 100 μL of prepared Nation solution, and disperse it uniformly under ultrasound for 2 h. Then pipette 18 μL of the solution onto the glassy carbon electrode and dry it naturally.

(2)配制1.0M的氢氧化钾溶液作为电催化的电解液，通入氮气赶跑空气，用1.0M的氢氧化钾溶液清洗析氢玻碳电极的电极表面，接着将析氢玻碳电极、Ag/AgCl电极、铂电极接上电化学工作站，在电解液中测得该电极材料电催化析氢的性能，该材料Tafel斜率为98mV dec-1，在电流密度为10mA cm-2的过电位为225mV。且在经过1000圈CV测试后的LSV曲线和CV测试之前的LSV曲线偏差不大，说明该材料拥有良好的稳定性。(2) prepare a 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introduce nitrogen to drive off the air, clean the electrode surface of the hydrogen-evolution glassy carbon electrode with a 1.0M potassium hydroxide solution, and then combine the hydrogen-evolving glassy carbon electrode, Ag The electrocatalytic hydrogen evolution performance of the electrode material was measured in the electrolyte. The Tafel slope of the material was 98mV dec -1 , and the overpotential at a current density of 10mA cm -2 was 225mV. . And the LSV curve after 1000 cycles of CV test has little deviation from the LSV curve before CV test, indicating that the material has good stability.

实施例3：Example 3:

四硫代钼酸铵0.5mmolAmmonium tetrathiomolybdate 0.5mmol

硫脲2.5mmolThiourea 2.5mmol

去离子水10mLDeionized water 10mL

析氢材料通过如下步骤的制备方法制备：The hydrogen evolution material is prepared by the preparation method of the following steps:

将将0.5mmol四硫代钼酸铵、2.5mmol硫脲溶于10mL去离子水中，在超声震荡仪中超声5min至搅拌溶解。见溶液中无固体颗粒后，转移至高压反应釜，放入8mm×8mm×1mm的泡沫镍，180℃下水热12h。取出Mo-S/NF经处理后放入电阻炉中，通入氮气，在400℃的温度下煅烧2h，最终得到Mo-S/NF析氢材料。Dissolve 0.5 mmol of ammonium tetrathiomolybdate and 2.5 mmol of thiourea in 10 mL of deionized water, and sonicate for 5 min in an ultrasonic oscillator to dissolve with stirring. After seeing that there are no solid particles in the solution, transfer it to a high-pressure reactor, put 8mm×8mm×1mm nickel foam, and heat it with water at 180°C for 12h. The Mo-S/NF was taken out and put into a resistance furnace after treatment. Nitrogen was introduced, and it was calcined at a temperature of 400 °C for 2 h to finally obtain a Mo-S/NF hydrogen evolution material.

应用实施例3：Application Example 3:

将实施例3的Mo-S/NF析氢材料进行研磨，将玻碳电极表面使用0.05μm的氧化铝研磨干净，除去残留样品，使用乙醇和去离子水冲洗干净，晾干。The Mo-S/NF hydrogen evolution material of Example 3 was ground, and the surface of the glassy carbon electrode was ground with 0.05 μm alumina to remove residual samples, rinsed with ethanol and deionized water, and dried.

(1)用无水甲醇配Nation溶液0.5wt％。称取1mg Mo-S/NF析氢材料溶解在100μL配制好的Nation溶液中，在超声下均匀分散2h。然后再将该溶液吸取18μL于玻碳电极上，自然晾干。(1) Prepare 0.5wt% Nation solution with anhydrous methanol. Weigh 1 mg of Mo-S/NF hydrogen evolution material, dissolve it in 100 μL of prepared Nation solution, and disperse it uniformly under ultrasound for 2 h. Then pipette 18 μL of the solution onto the glassy carbon electrode and dry it naturally.

(2)配制1.0M的氢氧化钾溶液作为电催化的电解液，通入氮气赶跑空气，用1.0M的氢氧化钾溶液清洗析氢玻碳电极的电极表面，接着将析氢玻碳电极、Ag/AgCl电极、铂电极接上电化学工作站，在电解液中测得该电极材料电催化析氢的性能，该材料Tafel斜率为113mV dec-1，在电流密度为10mA cm-2的过电位为256mV。且在经过1000圈CV测试后的LSV曲线和CV测试之前的LSV曲线偏差不大，说明该材料拥有良好的稳定性。(2) prepare a 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introduce nitrogen to drive off the air, clean the electrode surface of the hydrogen-evolution glassy carbon electrode with a 1.0M potassium hydroxide solution, and then combine the hydrogen-evolving glassy carbon electrode, Ag The electrocatalytic hydrogen evolution performance of the electrode material was measured in the electrolyte. The Tafel slope of the material was 113mV dec -1 , and the overpotential at a current density of 10mA cm -2 was 256mV. . And the LSV curve after 1000 cycles of CV test has little deviation from the LSV curve before CV test, indicating that the material has good stability.

对比例1：Comparative Example 1:

改变四硫代钼酸铵与硫脲的摩尔比为1:10：Change the molar ratio of ammonium tetrathiomolybdate to thiourea to 1:10:

四硫代钼酸铵0.5mmolAmmonium tetrathiomolybdate 0.5mmol

硫脲5mmolThiourea 5mmol

去离子水10mLDeionized water 10mL

析氢材料通过如下步骤的制备方法制备：The hydrogen evolution material is prepared by the preparation method of the following steps:

将0.5mmol四硫代钼酸铵、5mmol硫脲溶于10mL去离子水中，在超声震荡仪中超声5min至搅拌溶解。见溶液中无固体颗粒后，转移至高压反应釜，放入8mm×8mm×1mm的泡沫镍，180℃下水热12h。取出Mo-S/NF经处理后放入电阻炉中，通入氮气，在400℃的温度下煅烧2h，最终得到Mo-S/NF析氢材料。Dissolve 0.5 mmol of ammonium tetrathiomolybdate and 5 mmol of thiourea in 10 mL of deionized water, and sonicate in an ultrasonic oscillator for 5 min until stirring to dissolve. After seeing that there are no solid particles in the solution, transfer it to a high-pressure reactor, put 8mm×8mm×1mm nickel foam, and heat it with water at 180°C for 12h. The Mo-S/NF was taken out and put into a resistance furnace after treatment. Nitrogen was introduced, and it was calcined at a temperature of 400 °C for 2 h to finally obtain a Mo-S/NF hydrogen evolution material.

应用对比例1：Application Comparative Example 1:

将对比例1的Mo-S/NF析氢材料进行研磨，将玻碳电极表面使用0.05μm的氧化铝研磨干净，除去残留样品，使用乙醇和去离子水冲洗干净，晾干。The Mo-S/NF hydrogen evolution material of Comparative Example 1 was ground, and the surface of the glassy carbon electrode was ground with 0.05 μm alumina to remove residual samples, rinsed with ethanol and deionized water, and dried.

(1)用无水甲醇配Nation溶液0.5wt％。称取1mg Mo-S/NF析氢材料溶解在100μL配制好的Nation溶液中，在超声下均匀分散两个小时。然后再将该溶液吸取18μL于玻碳电极上，自然晾干。(1) Prepare 0.5wt% Nation solution with anhydrous methanol. Weigh 1 mg of Mo-S/NF hydrogen evolution material, dissolve it in 100 μL of prepared Nation solution, and disperse it uniformly for two hours under ultrasound. Then pipette 18 μL of the solution onto the glassy carbon electrode and dry it naturally.

(2)配制1.0M的氢氧化钾溶液作为电催化的电解液，通入氮气赶跑空气，用1.0M的氢氧化钾溶液清洗析氢玻碳电极的电极表面，接着将析氢玻碳电极、Ag/AgCl电极、铂电极接上电化学工作站，在电解液中测得该电极材料电催化析氢的性能，该材料Tafel斜率为171mV dec-1，在电流密度为10mA cm-2的过电位为419mV。在经过1000圈CV测试后的LSV曲线和CV测试之前的LSV曲线产生一定的偏差，说明该材料稳定性不好。(2) prepare a 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introduce nitrogen to drive off the air, clean the electrode surface of the hydrogen-evolution glassy carbon electrode with a 1.0M potassium hydroxide solution, and then combine the hydrogen-evolving glassy carbon electrode, Ag The electrocatalytic hydrogen evolution performance of the electrode material was measured in the electrolyte. The Tafel slope of the material was 171mV dec -1 , and the overpotential at a current density of 10mA cm -2 was 419mV. . There is a certain deviation between the LSV curve after the 1000-cycle CV test and the LSV curve before the CV test, indicating that the material has poor stability.

对比例2：Comparative Example 2:

改变四硫代钼酸铵与硫脲的摩尔比为2:1。Change the molar ratio of ammonium tetrathiomolybdate to thiourea to 2:1.

四硫代钼酸铵1mmolAmmonium tetrathiomolybdate 1mmol

硫脲0.5mmolThiourea 0.5mmol

去离子水10mLDeionized water 10mL

析氢材料通过如下步骤的制备方法制备：The hydrogen evolution material is prepared by the preparation method of the following steps:

将1mmol四硫代钼酸铵、0.5mmol硫脲溶于10mL去离子水中，在超声震荡仪中超声5min至搅拌溶解。见溶液中无固体颗粒后，转移至高压反应釜，放入8mm×8mm×1mm的泡沫镍，180℃下水热12h。取出Mo-S/NF经处理后放入电阻炉中，通入氮气，在400℃的温度下煅烧2h，最终得到Mo-S/NF析氢材料。1 mmol of ammonium tetrathiomolybdate and 0.5 mmol of thiourea were dissolved in 10 mL of deionized water, and sonicated for 5 min in an ultrasonic oscillator until they were dissolved by stirring. After seeing that there are no solid particles in the solution, transfer it to a high-pressure reactor, put 8mm×8mm×1mm nickel foam, and heat it with water at 180°C for 12h. The Mo-S/NF was taken out and put into a resistance furnace after treatment. Nitrogen was introduced, and it was calcined at a temperature of 400 °C for 2 h to finally obtain a Mo-S/NF hydrogen evolution material.

应用对比例2：Application Comparative Example 2:

将对比例2的Mo-S/NF析氢材料进行研磨，将玻碳电极表面使用0.05μm的氧化铝研磨干净，除去残留样品，使用乙醇和去离子水冲洗干净，晾干。The Mo-S/NF hydrogen evolution material of Comparative Example 2 was ground, and the surface of the glassy carbon electrode was ground with 0.05 μm alumina to remove residual samples, rinsed with ethanol and deionized water, and dried.

(1)用无水甲醇配Nation溶液0.5wt％。称取1mg Mo-S/NF析氢材料溶解在100μL配制好的Nation溶液中，在超声下均匀分散2。然后再将该溶液吸取18μL于玻碳电极上，自然晾干。(1) Prepare 0.5wt% Nation solution with anhydrous methanol. Weigh 1 mg of Mo-S/NF hydrogen evolution material, dissolve it in 100 μL of prepared Nation solution, and uniformly disperse it under ultrasonication. Then pipette 18 μL of the solution onto the glassy carbon electrode and dry it naturally.

(2)配制1.0M的氢氧化钾溶液作为电催化的电解液，通入氮气赶跑空气，用1.0M的氢氧化钾溶液清洗析氢玻碳电极的电极表面，接着将析氢玻碳电极、Ag/AgCl电极、铂电极接上电化学工作站，在电解液中测得该电极材料电催化析氢的性能，该材料Tafel斜率为162mV dec-1，在电流密度为10mA cm-2的过电位为303mV。且在经过1000圈CV测试后的LSV曲线和CV测试之前的LSV曲线产生一定的偏差，说明该材料稳定性不好。(2) prepare a 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introduce nitrogen to drive off the air, clean the electrode surface of the hydrogen-evolution glassy carbon electrode with a 1.0M potassium hydroxide solution, and then combine the hydrogen-evolving glassy carbon electrode, Ag The electrocatalytic hydrogen evolution performance of the electrode material was measured in the electrolyte. The Tafel slope of the material was 162mV dec -1 , and the overpotential at a current density of 10mA cm -2 was 303mV. . And there is a certain deviation between the LSV curve after 1000 cycles of CV test and the LSV curve before CV test, indicating that the material has poor stability.

由实施例1-3和对比例1-2可以看出，当四硫代钼酸铵与硫脲的摩尔比为1:(1-5)时，Mo-S/NF析氢材料的电化学性能最好，提高其中任一原料的量都会导致材料性能的变差。故改变原料外其他变量时应控制四硫代钼酸铵与硫脲摩尔比为1:(1-5)。It can be seen from Examples 1-3 and Comparative Examples 1-2 that when the molar ratio of ammonium tetrathiomolybdate and thiourea is 1:(1-5), the electrochemical performance of Mo-S/NF hydrogen evolution material Preferably, increasing the amount of either of these materials will result in a deterioration of the material properties. Therefore, the molar ratio of ammonium tetrathiomolybdate and thiourea should be controlled to be 1:(1-5) when other variables other than raw materials are changed.

实施例4：Example 4:

一种Mo-S/NF析氢材料的制备方法，该方法包括以下步骤：A preparation method of Mo-S/NF hydrogen evolution material, the method comprises the following steps:

1)将四硫代钼酸铵、硫脲与水混合，并进行超声分散，得到混合溶液；1) ammonium tetrathiomolybdate, thiourea and water are mixed, and ultrasonic dispersion is carried out to obtain a mixed solution;

2)将混合溶液加入至反应釜中，并在反应釜中放入泡沫镍作为载体，经水热反应后得到Mo-S/NF；2) adding the mixed solution into the reactor, and putting nickel foam into the reactor as a carrier to obtain Mo-S/NF after hydrothermal reaction;

3)将Mo-S/NF在无氧条件下进行煅烧，即得到Mo-S/NF析氢材料。析氢材料中，Mo在泡沫镍中的负载量为17％。3) calcining the Mo-S/NF under an oxygen-free condition to obtain a Mo-S/NF hydrogen evolution material. In the hydrogen evolution material, the loading of Mo in nickel foam is 17%.

步骤1)中，四硫代钼酸铵与硫脲的摩尔比为1:1，四硫代钼酸铵的摩尔量与水的体积之比为1mmol:25mL。超声分散的时间为5min，超声分散后得到澄清的混合溶液。In step 1), the molar ratio of ammonium tetrathiomolybdate to thiourea is 1:1, and the ratio of the molar amount of ammonium tetrathiomolybdate to the volume of water is 1 mmol:25 mL. The ultrasonic dispersion time was 5 min, and a clear mixed solution was obtained after ultrasonic dispersion.

步骤2)中，水热反应中，温度为200℃，时间为10h。In step 2), in the hydrothermal reaction, the temperature is 200°C and the time is 10h.

步骤3)中，煅烧在电阻炉中进行，煅烧过程中通入氮气。煅烧中，温度为500℃，时间为2h。In step 3), calcination is carried out in a resistance furnace, and nitrogen gas is introduced into the calcination process. During calcination, the temperature was 500°C and the time was 2h.

Mo-S/NF析氢材料在电催化析氢反应中应用时，将Mo-S/NF析氢材料与Nafion溶液混合均匀后，滴涂于玻碳电极上，干燥后得到析氢玻碳电极，作为电催化析氢反应中的工作电极。When the Mo-S/NF hydrogen evolution material is used in the electrocatalytic hydrogen evolution reaction, the Mo-S/NF hydrogen evolution material and Nafion solution are mixed uniformly, then drop-coated on the glassy carbon electrode, and dried to obtain a hydrogen evolution glassy carbon electrode, which is used as an electrocatalyst Working electrode in hydrogen evolution reaction.

实施例5：Example 5:

一种Mo-S/NF析氢材料的制备方法，该方法包括以下步骤：A preparation method of Mo-S/NF hydrogen evolution material, the method comprises the following steps:

1)将四硫代钼酸铵、硫脲与水混合，并进行超声分散，得到混合溶液；1) ammonium tetrathiomolybdate, thiourea and water are mixed, and ultrasonic dispersion is carried out to obtain a mixed solution;

2)将混合溶液加入至反应釜中，并在反应釜中放入泡沫镍作为载体，经水热反应后得到Mo-S/NF；2) adding the mixed solution into the reactor, and putting nickel foam into the reactor as a carrier to obtain Mo-S/NF after hydrothermal reaction;

3)将Mo-S/NF在无氧条件下进行煅烧，即得到Mo-S/NF析氢材料。析氢材料中，Mo在泡沫镍中的负载量为20％。3) calcining the Mo-S/NF under an oxygen-free condition to obtain a Mo-S/NF hydrogen evolution material. In the hydrogen evolution material, the loading of Mo in nickel foam is 20%.

步骤1)中，四硫代钼酸铵与硫脲的摩尔比为1:5，四硫代钼酸铵的摩尔量与水的体积之比为1mmol:15mL。超声分散的时间为10min，超声分散后得到澄清的混合溶液。In step 1), the molar ratio of ammonium tetrathiomolybdate to thiourea is 1:5, and the ratio of the molar amount of ammonium tetrathiomolybdate to the volume of water is 1 mmol:15 mL. The time of ultrasonic dispersion was 10 min, and a clear mixed solution was obtained after ultrasonic dispersion.

步骤2)中，水热反应中，温度为150℃，时间为15h。In step 2), in the hydrothermal reaction, the temperature is 150°C and the time is 15h.

步骤3)中，煅烧在电阻炉中进行，煅烧过程中通入氮气。煅烧中，温度为300℃，时间为4h。In step 3), calcination is carried out in a resistance furnace, and nitrogen gas is introduced into the calcination process. During calcination, the temperature was 300°C and the time was 4h.

Mo-S/NF析氢材料在电催化析氢反应中应用时，将Mo-S/NF析氢材料与Nafion溶液混合均匀后，滴涂于玻碳电极上，干燥后得到析氢玻碳电极，作为电催化析氢反应中的工作电极。When the Mo-S/NF hydrogen evolution material is used in the electrocatalytic hydrogen evolution reaction, the Mo-S/NF hydrogen evolution material and Nafion solution are mixed uniformly, then drop-coated on the glassy carbon electrode, and dried to obtain a hydrogen evolution glassy carbon electrode, which is used as an electrocatalyst Working electrode in hydrogen evolution reaction.

实施例6：Example 6:

一种Mo-S/NF析氢材料的制备方法，该方法包括以下步骤：A preparation method of Mo-S/NF hydrogen evolution material, the method comprises the following steps:

1)将四硫代钼酸铵、硫脲与水混合，并进行超声分散，得到混合溶液；1) ammonium tetrathiomolybdate, thiourea and water are mixed, and ultrasonic dispersion is carried out to obtain a mixed solution;

2)将混合溶液加入至反应釜中，并在反应釜中放入泡沫镍作为载体，经水热反应后得到Mo-S/NF；2) adding the mixed solution into the reactor, and putting nickel foam into the reactor as a carrier to obtain Mo-S/NF after hydrothermal reaction;

3)将Mo-S/NF在无氧条件下进行煅烧，即得到Mo-S/NF析氢材料。析氢材料中，Mo在泡沫镍中的负载量为15％。3) calcining the Mo-S/NF under an oxygen-free condition to obtain a Mo-S/NF hydrogen evolution material. In the hydrogen evolution material, the loading of Mo in nickel foam is 15%.

步骤1)中，四硫代钼酸铵与硫脲的摩尔比为1:3，四硫代钼酸铵的摩尔量与水的体积之比为1mmol:20mL。超声分散的时间为7min，超声分散后得到澄清的混合溶液。In step 1), the molar ratio of ammonium tetrathiomolybdate to thiourea is 1:3, and the ratio of the molar amount of ammonium tetrathiomolybdate to the volume of water is 1 mmol:20 mL. The ultrasonic dispersion time was 7 min, and a clear mixed solution was obtained after ultrasonic dispersion.

步骤2)中，水热反应中，温度为170℃，时间为12h。In step 2), in the hydrothermal reaction, the temperature is 170°C and the time is 12h.

步骤3)中，煅烧在电阻炉中进行，煅烧过程中通入氮气。煅烧中，温度为400℃，时间为3h。In step 3), calcination is carried out in a resistance furnace, and nitrogen gas is introduced into the calcination process. During calcination, the temperature was 400°C and the time was 3h.

Mo-S/NF析氢材料在电催化析氢反应中应用时，将Mo-S/NF析氢材料与Nafion溶液混合均匀后，滴涂于玻碳电极上，干燥后得到析氢玻碳电极，作为电催化析氢反应中的工作电极。When the Mo-S/NF hydrogen evolution material is used in the electrocatalytic hydrogen evolution reaction, the Mo-S/NF hydrogen evolution material and Nafion solution are mixed uniformly, then drop-coated on the glassy carbon electrode, and dried to obtain a hydrogen evolution glassy carbon electrode, which is used as an electrocatalyst Working electrode in hydrogen evolution reaction.

上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。The foregoing description of the embodiments is provided to facilitate understanding and use of the invention by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications to these embodiments can be readily made, and the generic principles described herein can be applied to other embodiments without inventive step. Therefore, the present invention is not limited to the above-mentioned embodiments, and improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should all fall within the protection scope of the present invention.

Claims (10)

1. A preparation method of a Mo-S/NF hydrogen evolution material is characterized by comprising the following steps:
1) mixing ammonium tetrathiomolybdate and thiourea with water, and performing ultrasonic dispersion to obtain a mixed solution;
2) adding the mixed solution into a reaction kettle, adding foamed nickel serving as a carrier into the reaction kettle, and performing hydrothermal reaction to obtain Mo-S/NF;
3) and calcining the Mo-S/NF under an anaerobic condition to obtain the Mo-S/NF hydrogen evolution material.
2. The method for preparing a Mo-S/NF hydrogen evolution material according to claim 1, wherein in the step 1), the molar ratio of ammonium tetrathiomolybdate to thiourea is 1 (1-5), and the ratio of the molar amount of ammonium tetrathiomolybdate to the volume of water is 1mmol (15-25) mL.
3. The preparation method of the Mo-S/NF hydrogen evolution material as claimed in claim 1, wherein in the step 1), the ultrasonic dispersion time is 5-10min, and a clear mixed solution is obtained after the ultrasonic dispersion.
4. The method for preparing a Mo-S/NF hydrogen evolution material as claimed in claim 1, wherein in the step 2), the temperature is 150-200 ℃ and the time is 10-15h in the hydrothermal reaction.
5. The method for preparing the Mo-S/NF hydrogen evolution material as claimed in claim 1, wherein in the step 3), the calcination is performed in a resistance furnace, and nitrogen is introduced during the calcination.
6. The method as claimed in claim 1, wherein the temperature of the calcination step 3) is 300-500 ℃ and the time is 2-4 h.
7. A Mo-S/NF hydrogen evolution material, characterized in that it is prepared by a method according to any of claims 1 to 6.
8. The Mo-S/NF hydrogen evolution material as claimed in claim 7, wherein the loading of Mo in the hydrogen evolution material is 15-20% of that in foamed nickel.
9. Use of the Mo-S/NF hydrogen evolution material of claim 7 in electrocatalytic hydrogen evolution reactions.
10. The application of the Mo-S/NF hydrogen evolution material in the electrocatalytic hydrogen evolution reaction as claimed in claim 9, wherein in the application, the Mo-S/NF hydrogen evolution material is uniformly mixed with Nafion solution, and then is dripped on a glassy carbon electrode, and the glassy carbon electrode is dried to obtain the hydrogen evolution glassy carbon electrode which is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
CN202010151960.3A 2020-03-06 2020-03-06 A kind of Mo-S/NF hydrogen evolution material and its preparation method and application Pending CN111359636A (en)

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