CN108358181A - Hydrogen evolution reaction electrocatalyst of phosphide, preparation method and application - Google Patents
Hydrogen evolution reaction electrocatalyst of phosphide, preparation method and application Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于电化学催化剂领域，涉及一种磷化物析氢反应电催化剂及其制备方法和应用，可用于电解水这种能源存储与转换技术的电催化剂。The invention belongs to the field of electrochemical catalysts, and relates to a phosphide hydrogen evolution reaction electrocatalyst, a preparation method and an application thereof, and can be used as an electrocatalyst for energy storage and conversion technology such as electrolysis of water.
背景技术Background technique
当今世界，能源问题是人类社会发展的关键问题。随着化石能源的过渡使用，全球变暖、温室效应、空气污染等环境和污染问题变得日益严峻。为了实现人类的可持续发展，开发和利用经济、高效、洁净的新能源是21世纪世界能源科技的主题。目前，太阳能、风能和潮汐能等可再生能源备受世界关注，然而这些新能源发电属于不可控电源，存在间歇性和不稳定性等缺点。发展先进的电化学能源存储与转换技术，如燃料电池、金属-空气电池、电解水等，是解决问题的根本途径。In today's world, the energy issue is a key issue in the development of human society. With the excessive use of fossil energy, environmental and pollution problems such as global warming, greenhouse effect, and air pollution have become increasingly severe. In order to realize the sustainable development of mankind, the development and utilization of economical, efficient and clean new energy is the theme of world energy technology in the 21st century. At present, renewable energy sources such as solar energy, wind energy, and tidal energy are attracting worldwide attention. However, these new energy sources are uncontrollable power sources, which have shortcomings such as intermittent and instability. The fundamental way to solve the problem is to develop advanced electrochemical energy storage and conversion technologies, such as fuel cells, metal-air batteries, and electrolyzed water.
其中，电化学水解制氢是一种有效的且备受关注的方法，但其阴极析氢反应(HER)受到迟缓动力学的严重限制。因此，其需要催化剂来加速反应。但是，目前最为高效的催化剂依然是铂族的贵金属催化剂。贵金属的高价及稀缺等缺点又严重限制了其大力发展。Among them, electrochemical hydrolysis for hydrogen production is an efficient and attractive method, but its cathodic hydrogen evolution reaction (HER) is severely limited by sluggish kinetics. Therefore, it requires a catalyst to speed up the reaction. However, the most efficient catalysts are still noble metal catalysts of the platinum group. The high price and scarcity of precious metals have seriously restricted its vigorous development.
所以，为了提高电解水的电化学效率，寻找性能优越的阴极析氢催化剂以尽可能地降低成本，是电解水研究的难点，也是热点问题。Therefore, in order to improve the electrochemical efficiency of electrolyzed water, finding a cathodic hydrogen evolution catalyst with superior performance to reduce the cost as much as possible is a difficult point in the research of electrolyzed water, and it is also a hot issue.
发明内容Contents of the invention
本发明的一个目的是提供一种一磷化钌析氢反应电催化剂及其制备方法和应用，来改善现有最好的析氢反应电催化剂(Pt/C)价格昂贵和稳定性差等问题。该催化剂与Pt/C相比，不仅具更卓越的的氢析出(HER)催化性能和长期稳定性，而且还具有成本相对低廉和制备方法简单等优点。An object of the present invention is to provide a ruthenium phosphide hydrogen evolution reaction electrocatalyst and its preparation method and application, to improve the existing best hydrogen evolution reaction electrocatalyst (Pt/C) expensive and poor stability problems. Compared with Pt/C, the catalyst not only has more excellent hydrogen evolution (HER) catalytic performance and long-term stability, but also has the advantages of relatively low cost and simple preparation method.
本发明的第一个方面，提供了为了实现上述目的，本发明的技术方案如下：A first aspect of the present invention provides in order to achieve the above object, the technical solution of the present invention is as follows:
一种一磷化钌的析氢反应电催化剂，所述析氢反应电催化剂组成分子式为RuP。An electrocatalyst for the hydrogen evolution reaction of ruthenium phosphide, the molecular formula of the electrocatalyst for the hydrogen evolution reaction is RuP.
本发明的第二个方面，提供了一种析氢反应电催化剂的制备方法。所述制备方法是将RuCl3·3H2O通过低温磷化反应制备得到。The second aspect of the present invention provides a method for preparing an electrocatalyst for hydrogen evolution reaction. The preparation method is to prepare RuCl 3 ·3H 2 O through low-temperature phosphating reaction.
优选的，所述的制备方法，具体步骤如下：Preferably, described preparation method, specific steps are as follows:
将RuCl3·3H2O和NaH2PO2分别放在管式炉的下游和上游；Place RuCl 3 3H 2 O and NaH 2 PO 2 downstream and upstream of the tube furnace, respectively;
然后进行低温反应，得到所需析氢反应电催化剂。Then carry out the low-temperature reaction to obtain the desired hydrogen evolution reaction electrocatalyst.
该方法步骤简单，适合工业化大规模制备。The method has simple steps and is suitable for large-scale industrial preparation.
优选的，NaH2PO2和RuCl3·3H2O的质量比为5-10:1。Preferably, the mass ratio of NaH 2 PO 2 to RuCl 3 ·3H 2 O is 5-10:1.
优选的，所述的RuCl3·3H2O和NaH2PO2的距离相距5-10cm且中间位于炉子正中间，所述的低温反应过程的条件是400-500℃处理1-5h，氛围是惰性气氛，包括但不限于氩气，氮气，氦气。Preferably, the distance between RuCl 3 .3H 2 O and NaH 2 PO 2 is 5-10 cm and the middle is located in the middle of the furnace. The conditions of the low-temperature reaction process are 400-500°C for 1-5 hours, and the atmosphere is Inert atmosphere, including but not limited to argon, nitrogen, helium.
本发明的第三个方面，提供了一种析氢反应电催化剂的测试电解液pH范围，所述析氢反应电催化剂的电解液pH范围是0-14。The third aspect of the present invention provides a test electrolyte pH range of the hydrogen evolution reaction electrocatalyst, the electrolyte pH range of the hydrogen evolution reaction electrocatalyst is 0-14.
本发明的第四个方面，提供了一种析氢反应电催化剂在电解水中的应用，所述电解水阳极催化剂是氧化钌，所述电解水装置中的电解液是1M KOH。The fourth aspect of the present invention provides an application of a hydrogen evolution reaction electrocatalyst in electrolyzed water, the anode catalyst for electrolyzed water is ruthenium oxide, and the electrolyte in the electrolyzed water device is 1M KOH.
本发明的第五个方面，提供了：A fifth aspect of the present invention provides:
RuP在用于减小金属Ru析氢反应电催化剂的10mA cm-2对应的过电位的应用。Application of RuP in reducing the overpotential corresponding to 10 mA cm -2 of metal Ru hydrogen evolution reaction electrocatalysts.
RuP在用于减小金属Ru析氢反应电催化剂的塔菲尔斜率的应用。Application of RuP in reducing the Tafel slope of metallic Ru electrocatalysts for the hydrogen evolution reaction.
RuP在用于增加金属Ru析氢反应电催化剂的交换电流密度的应用。Application of RuP in increasing the exchange current density of metallic Ru electrocatalysts for the hydrogen evolution reaction.
RuP在用于增加金属Ru析氢反应电催化剂的稳定性的应用。Application of RuP for increasing the stability of metallic Ru electrocatalysts for the hydrogen evolution reaction.
RuP在用于减小金属Ru的电子分布从而增加Ru的价态的应用。RuP is used to reduce the electron distribution of metal Ru to increase the valence state of Ru.
RuP在用于超过标准析氢反应电催化剂Pt/C的10mA cm-2对应的过电位的应用。Application of RuP at an overpotential corresponding to 10 mA cm for exceeding the standard hydrogen evolution reaction electrocatalyst Pt/C.
RuP在用于超过标准析氢反应电催化剂Pt/C的塔菲尔斜率的应用。Application of RuP for Tafel slope exceeding the standard hydrogen evolution reaction electrocatalyst Pt/C.
RuP在用于超过标准析氢反应电催化剂Pt/C的交换电流密度的应用。Application of RuP for exchange current densities exceeding the standard hydrogen evolution reaction electrocatalyst Pt/C.
RuP在用于超过标准析氢反应电催化剂Pt/C的稳定性的应用。Application of RuP for stability beyond the standard hydrogen evolution reaction electrocatalyst Pt/C.
综上所述，通过采用上述技术方案，本发明的有益效果如下：采用一步磷化法制备得到的RuP作为新型析氢反应电催化剂。通过对比RuP和金属Ru的氢析出反应性能，P的引入明显提高了其氢析出催化活性和稳定性。另外，本发明的析氢催化剂具有极其优异的氢析出(HER)活性和操作稳定性，均优于商业的贵金属氧化物Pt/C催化剂，可作为水电解的阴极电催化剂。本发明涉及到的RuP材料，制备方法非常简单，适合于大规模制备，有益于商业化。In summary, by adopting the above technical scheme, the beneficial effects of the present invention are as follows: RuP prepared by one-step phosphating method is used as a new electrocatalyst for hydrogen evolution reaction. By comparing the hydrogen evolution reaction performance of RuP and metal Ru, the introduction of P significantly improved its hydrogen evolution catalytic activity and stability. In addition, the hydrogen evolution catalyst of the present invention has extremely excellent hydrogen evolution (HER) activity and operational stability, both of which are superior to commercial noble metal oxide Pt/C catalysts, and can be used as a cathodic electrocatalyst for water electrolysis. The RuP material involved in the present invention has a very simple preparation method, is suitable for large-scale preparation, and is beneficial to commercialization.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only It is an embodiment of the present invention, and those skilled in the art can also obtain other drawings according to the provided drawings without creative work.
图1是RuP催化剂的X射线衍射(XRD)曲线图；Fig. 1 is the X-ray diffraction (XRD) curve figure of RuP catalyst;
图2是RuP的N2吸附-解吸(BET)曲线图；Fig. 2 is the N adsorption-desorption (BET) curve diagram of RuP;
图3是RuP的XPS全谱图；Figure 3 is the XPS full spectrum of RuP;
图4是Ru元素的3p轨道XPS结果图；Figure 4 is the 3p orbital XPS result map of Ru element;
图5是P元素的2p轨道XPS结果图；Figure 5 is the 2p orbital XPS result map of the P element;
图6是RuP粉体的SEM图；Fig. 6 is the SEM figure of RuP powder;
图7是RuP粉体的TEM图；Figure 7 is a TEM image of RuP powder;
图8是RuP，Ru和Pt/C催化剂在1M KOH溶液中的极化曲线图；Fig. 8 is the polarization curve figure of RuP, Ru and Pt/C catalyst in 1M KOH solution;
图9是由RuP，Ru和Pt/C催化剂在1M KOH溶液中的极化曲线图衍生出来的塔菲尔斜率图；Figure 9 is a Tafel slope diagram derived from the polarization curves of RuP, Ru and Pt/C catalysts in 1M KOH solution;
图10是由RuP，Ru和Pt/C催化剂在1M KOH溶液中的极化曲线图衍生出来的交换电流密度图；Figure 10 is an exchange current density diagram derived from the polarization curves of RuP, Ru and Pt/C catalysts in 1M KOH solution;
图11是RuP和Pt/C催化剂在1M KOH溶液中的稳定性测试图；Fig. 11 is the stability test figure of RuP and Pt/C catalyst in 1M KOH solution;
图12是RuP和Pt/C分别作为阴极催化剂与RuO2阳极催化剂组成的全解水装置在1MKOH溶液中的电解水性能图。Fig. 12 is the electrolytic water performance diagram of the total water splitting device composed of RuP and Pt/C as cathode catalyst and RuO2 anode catalyst respectively in 1M KOH solution.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。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。The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
本实施例提供一种析氢反应电催化剂RuP的制备方法，具体步骤如下：称取0.1g的RuCl3·3H2O和1g的NaH2PO2分别放在管式炉的下游和上游，两者相距7cm且中间位于炉子正中间。然后将其在氩气气氛下加热至400℃煅烧2h，得到所需析氢反应电催化剂。This embodiment provides a method for preparing RuP, an electrocatalyst for hydrogen evolution reaction. The specific steps are as follows: Weigh 0.1 g of RuCl 3 3H 2 O and 1 g of NaH 2 PO 2 and place them in the downstream and upstream of the tube furnace respectively. 7cm apart and the middle is in the middle of the stove. Then it was heated to 400 °C and calcined for 2 h under an argon atmosphere to obtain the desired hydrogen evolution reaction electrocatalyst.
实施例2Example 2
本实施例提供一种析氢反应电催化剂RuP的制备方法，具体步骤如下：称取0.1g的RuCl3·3H2O和0.5g的NaH2PO2分别放在管式炉的下游和上游，两者相距7cm且中间位于炉子正中间。然后将其在氩气气氛下加热至400℃煅烧2h，得到析氢反应电催化剂。该反应催化剂与实施例1相比，10mA cm-2对应的过电位变大，塔菲尔斜率变大，交换电流密度变小，稳定性变差。This embodiment provides a method for preparing RuP, an electrocatalyst for hydrogen evolution reaction. The specific steps are as follows: Weigh 0.1 g of RuCl 3 3H 2 O and 0.5 g of NaH 2 PO 2 and place them in the downstream and upstream of the tube furnace respectively. The distance between them is 7cm and the middle is located in the middle of the stove. Then it was heated to 400°C and calcined for 2 h under an argon atmosphere to obtain a hydrogen evolution reaction electrocatalyst. Compared with Example 1, the reaction catalyst has larger overpotential corresponding to 10 mA cm -2 , larger Tafel slope, smaller exchange current density and worse stability.
实施例3Example 3
本实施例提供一种析氢反应电催化剂RuP的制备方法，具体步骤如下：称取0.1g的RuCl3·3H2O和0.5g的NaH2PO2分别放在管式炉的下游和上游，两者相距10cm且中间位于炉子正中间。然后将其在氩气气氛下加热至400℃煅烧2h，得到析氢反应电催化剂。该反应催化剂与实施例1相比，10mA cm-2对应的过电位变大，塔菲尔斜率变大，交换电流密度变小，稳定性变差。This example provides a method for preparing RuP, an electrocatalyst for hydrogen evolution reaction. The specific steps are as follows: Weigh 0.1 g of RuCl 3 3H 2 O and 0.5 g of NaH 2 PO 2 and place them in the downstream and upstream of the tube furnace respectively. The distance between them is 10cm and the middle is located in the middle of the stove. Then it was heated to 400°C and calcined for 2 h under an argon atmosphere to obtain a hydrogen evolution reaction electrocatalyst. Compared with Example 1, the overpotential corresponding to 10mA cm -2 of this reaction catalyst becomes larger, the Tafel slope becomes larger, the exchange current density becomes smaller, and the stability becomes worse.
实施例4Example 4
本实施例提供一种析氢反应电催化剂RuP的制备方法，具体步骤如下：称取0.1g的RuCl3·3H2O和0.5g的NaH2PO2分别放在管式炉的下游和上游，两者相距7cm且中间位于炉子正中间。然后将其在氩气气氛下加热至500℃煅烧2h，得到析氢反应电催化剂。该反应催化剂与实施例1相比，10mA cm-2对应的过电位变大，塔菲尔斜率变大，交换电流密度变小，稳定性变差。This embodiment provides a method for preparing RuP, an electrocatalyst for hydrogen evolution reaction. The specific steps are as follows: Weigh 0.1 g of RuCl 3 3H 2 O and 0.5 g of NaH 2 PO 2 and place them in the downstream and upstream of the tube furnace respectively. The distance between them is 7cm and the middle is located in the middle of the stove. Then it was heated to 500° C. for 2 h under an argon atmosphere and calcined to obtain a hydrogen evolution reaction electrocatalyst. Compared with Example 1, the reaction catalyst has larger overpotential corresponding to 10 mA cm -2 , larger Tafel slope, smaller exchange current density and worse stability.
对照例1：按照实施例1中的制备方法，不加入NaH2PO2，将0.1g的RuCl3·3H2O直接放到管式炉中部，然后将其在氢氩气氛下加热至400℃煅烧2h，可以相应地制备得到RuO2析氢反应电催化剂。另外，商业Pt/C催化剂也是被使用的。Comparative Example 1: According to the preparation method in Example 1, without adding NaH 2 PO 2 , put 0.1g of RuCl 3 ·3H 2 O directly into the middle of the tube furnace, and then heat it to 400°C under a hydrogen-argon atmosphere After calcination for 2 h, the RuO 2 hydrogen evolution reaction electrocatalyst can be prepared accordingly. In addition, commercial Pt/C catalysts are also used.
为了进一步说明本发明制备的析氢反应电催化剂RuP具有良好的性能，发明进行了如下的应用测试：In order to further illustrate that the hydrogen evolution reaction electrocatalyst RuP prepared by the present invention has good performance, the invention has carried out the following application tests:
1.材料的表征如下1. The characterization of the material is as follows
RuP样品晶体结构由室温X射线衍射(XRD)在10-90°范围内以间隔0.02°进行测试。The crystal structure of the RuP samples was tested by room temperature X-ray diffraction (XRD) in the range of 10–90° at intervals of 0.02°.
获得的衍射曲线通过一般结构分析***(GSAS)和EXPGUI接口进行分析。样品比表面积和孔径分布通过BELSORP||装置在液氮的沸腾温度下，基于N2吸附-解吸(BET)曲线来获得。The obtained diffraction curves were analyzed by General Structural Analysis System (GSAS) and EXPGUI interface. Specific surface area and pore size distribution of samples were obtained by BELSORP|| device at the boiling temperature of liquid nitrogen, based on N2 adsorption-desorption (BET) curves.
对RuP粉体进行X射线光电子能谱测试，分析其表面化学组成和化学价态。The RuP powder was tested by X-ray photoelectron spectroscopy to analyze its surface chemical composition and chemical valence state.
RuP粉体的形貌可以通过扫描电镜图和G2T20电子显微镜测试获得。The morphology of RuP powder can be obtained by scanning electron microscope and G2T20 electron microscope test.
采用本发明所制备的催化剂制备电极、评价电极氢析出(HER)催化性能，过程如下：The catalyst prepared by the present invention is used to prepare electrodes and evaluate the hydrogen evolution (HER) catalytic performance of the electrodes. The process is as follows:
1.催化剂浆料的制备：将RuP粉体与一定量的导电炭黑混合(导电炭黑质量分数85％，起着导电和载体的作用，几乎没有催化作用)分散在乙醇或者其它有机溶剂中，再向其中加入适量Nafion(质量分数5％)溶液，(催化剂浓度为1.5mg/mL，Nafion在溶液中的浓度为0.2mg/mL)，然后超声振荡使混合均匀得到制备催化剂的浆料。1. Preparation of catalyst slurry: Mix RuP powder with a certain amount of conductive carbon black (the mass fraction of conductive carbon black is 85%, which plays the role of conductivity and carrier, and has almost no catalytic effect) and disperses them in ethanol or other organic solvents , then add an appropriate amount of Nafion (mass fraction 5%) solution thereto, (catalyst concentration is 1.5mg/mL, the concentration of Nafion in the solution is 0.2mg/mL), then ultrasonic vibration makes mixing uniform to obtain the slurry for preparing catalyst.
2.电极制备：将上述制备的催化剂浆料，用微量注射器移取一定量到旋转圆盘电极(RDE)上，使其在RDE上的负载量为0.232mg/cm2，然后放在空气中自然吹干。2. Electrode preparation: Pipette a certain amount of the catalyst slurry prepared above onto the rotating disk electrode (RDE) with a micro-syringe, so that the loading amount on the RDE is 0.232 mg/cm 2 , and then place it in the air Blow dry naturally.
3.电极活性的测量：将已制备好的电极装到旋转圆盘装置(Pine公司)上进行电化学测试。3. Measurement of electrode activity: The prepared electrode was mounted on a rotating disk device (Pine Company) for electrochemical testing.
测试的过程如下：The testing process is as follows:
1)电化学测试的体系为三电极体系(玻碳电极为工作电极，铂片或铂丝为对电极，Ag/AgCl为参比电极)，电解液为1M KOH,1M PBS,0.5M H2SO4。1) The electrochemical test system is a three-electrode system (glassy carbon electrode is the working electrode, platinum sheet or platinum wire is the counter electrode, Ag/AgCl is the reference electrode), and the electrolyte is 1M KOH, 1M PBS, 0.5MH 2 SO 4 .
2)在测试之前，向反应器中连续通氩气30～60min，以保证电解质溶液被氧气饱和，通气流量为150～250mL/min。在测试过程中氧气也一直保持通入。2) Before the test, continuously flow argon gas into the reactor for 30-60 minutes to ensure that the electrolyte solution is saturated with oxygen, and the flow rate of the gas flow is 150-250 mL/min. Oxygen was also kept flowing during the test.
3)评价氢析出(HER)催化活性，要进行极化曲线测试(LSV)，电压扫描范围为0.2～1V，扫描速度为5mV/s，旋转速度为1600rpm。3) To evaluate the catalytic activity of hydrogen evolution (HER), a polarization curve test (LSV) should be carried out. The voltage scanning range is 0.2-1V, the scanning speed is 5mV/s, and the rotation speed is 1600rpm.
4)评价催化稳定性，要进行恒电流法测试(固定10mA cm-2不变)观察电压随时间的变化关系来考察催化剂稳定性。4) To evaluate the catalytic stability, a galvanostatic test (fixed at 10mA cm −2 ) should be carried out to observe the relationship between the voltage and time to investigate the stability of the catalyst.
表征结果如下：The characterization results are as follows:
1.XRD表征1. XRD characterization
图1是RuP的室温下10～90°范围内测试的XRD图谱。从图中可以看出，其呈现出良好的正交晶系的RuP相结构。其中31.91°,44.02°and 46.02°三个主峰，分别对应于(011)，(112)和(211)晶面。Figure 1 is the XRD pattern of RuP tested in the range of 10-90° at room temperature. It can be seen from the figure that it presents a good orthorhombic RuP phase structure. Among them, the three main peaks at 31.91°, 44.02° and 46.02° correspond to (011), (112) and (211) crystal planes, respectively.
2.BET表征2. BET characterization
图2是RuP的N2吸附-解吸(BET)曲线，可以计算得出其比表面积为4.6m2g-1。Figure 2 is the N 2 adsorption-desorption (BET) curve of RuP, and its specific surface area can be calculated to be 4.6m 2 g -1 .
3.XPS分析3.XPS analysis
为了探究RuP的表面化学组成和化学价态，对RuP进行了XPS测试。图3证明了Ru，P，O三元素的存在。从图4可以看出，钌的3p3/2和3p1/2峰分别在462.2和484.4eV结合能处，与金属Ru相比，其向高结合能处偏移，证明了RuP的存在。对于P的2p峰主要有两个大区域：一个是结合能在130到131eV，代表磷化物信号；一个是结合能在134eV左右，代表磷酸盐物种。从图5可以看出，磷化物信号的存在进一步证实了RuP的形成。In order to explore the surface chemical composition and chemical valence state of RuP, XPS tests were carried out on RuP. Figure 3 proves the existence of Ru, P, O three elements. It can be seen from Figure 4 that the 3p3/2 and 3p1/2 peaks of ruthenium are at the binding energy of 462.2 and 484.4eV, respectively. Compared with metal Ru, it shifts to the high binding energy, which proves the existence of RuP. For the 2p peak of P, there are mainly two large regions: one is the binding energy between 130 and 131eV, representing the phosphide signal; the other is the binding energy around 134eV, representing the phosphate species. As can be seen from Figure 5, the presence of phosphide signals further confirms the formation of RuP.
4.SEM和TEM表征4. SEM and TEM characterization
图6和图7分别为RuP的SEM图和TEM图。从图中可以看出，RuP的形貌为10-30纳米粒子组成的大的微米粒子。从图7的插图，可以看出，晶格条纹为0.206nm，对应于RuP(112)晶面，进一步证明了RuP的形成。Figure 6 and Figure 7 are the SEM and TEM images of RuP, respectively. It can be seen from the figure that the morphology of RuP is a large micron particle composed of 10-30 nanometer particles. From the inset of Fig. 7, it can be seen that the lattice fringe is 0.206 nm, corresponding to the RuP (112) crystal plane, further proving the formation of RuP.
5.HER电催化活性表征5. Characterization of HER electrocatalytic activity
图8是RuP，Ru和Pt/C在1M KOH中HER的极化曲线图。从图中可以看出，RuP的初始过电位和10mA cm-2对应的过电位都明显小于Ru和Pt/C，说明在RuP可以显著的提高HER电催化活性。Fig. 8 is the HER polarization curves of RuP, Ru and Pt/C in 1M KOH. It can be seen from the figure that the initial overpotential of RuP and the corresponding overpotential of 10mA cm -2 are significantly smaller than those of Ru and Pt/C, indicating that RuP can significantly improve the electrocatalytic activity of HER.
图9和图10分别为RuP，Ru和Pt/C由其1M KOH中HER的极化曲线图衍生得出的Tafel斜率图和交换电流密度图。RuP的Tafel斜率明显小于金属Ru，略小于Pt/C，说明RuP更快的反应动力学，更好的HER催化活性。从交换电流密度图，可以看出RuP交换电流密度远远超过金属Ru和Pt/C，揭示了RuP更优异的本征催化活性。Figure 9 and Figure 10 are the Tafel slope diagram and the exchange current density diagram derived from the polarization curve diagram of HER in 1M KOH for RuP, Ru and Pt/C, respectively. The Tafel slope of RuP is significantly smaller than that of metallic Ru and slightly smaller than that of Pt/C, indicating the faster reaction kinetics of RuP and better catalytic activity for HER. From the exchange current density diagram, it can be seen that the exchange current density of RuP far exceeds that of metal Ru and Pt/C, revealing the superior intrinsic catalytic activity of RuP.
6.HER电催化稳定性表征6. Characterization of HER electrocatalytic stability
图11为RuP和Pt/C的恒电流法稳定性测试。通过固定10mA cm-2不变，观察电压随时间的变化关系来考察催化剂稳定性。很明显可以看出，经过100h的测试，Pt/C衰减很明显，而RuP几乎不变，说明其优异的稳定性。Figure 11 is the galvanostatic stability test of RuP and Pt/C. By fixing 10mA cm -2 constant and observing the relationship between voltage and time, the stability of the catalyst was investigated. It can be clearly seen that after 100h of testing, Pt/C decays significantly, while RuP is almost unchanged, indicating its excellent stability.
7.全解水性能表征7. Characterization of total water splitting performance
通过以上的表征实验，可以看出RuP具有卓越的HER电催化活性和稳定性，不仅在各方面远远超过了金属Ru，而且也超过了经典的Pt/C商业催化剂。当作为实际的电解水阴极时，RuP又表现出更好的电解水性能，10mA cm-2对应的操作电压仅有1.49V，使其成为电解水装置中极具商业化潜力的阴极电催化剂。Through the above characterization experiments, it can be seen that RuP has excellent electrocatalytic activity and stability for HER, not only far surpassing metal Ru in all aspects, but also surpassing the classic Pt/C commercial catalyst. When used as a practical water electrolysis cathode, RuP exhibits better water electrolysis performance, and the operating voltage corresponding to 10mA cm -2 is only 1.49V, making it a cathode electrocatalyst with great commercial potential in water electrolysis devices.
本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。对于实施例公开的装置而言，由于其与实施例公开的方法相对应，所以描述的比较简单，相关之处参见方法部分说明即可。Each embodiment in this specification is described in a progressive manner, each embodiment focuses on the difference from other embodiments, and the same and similar parts of each embodiment can be referred to each other. As for the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and for the related part, please refer to the description of the method part.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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| CN110860301A (en) * | 2019-11-26 | 2020-03-06 | 中国科学技术大学 | Ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst, preparation method thereof and application of dual-functional electrocatalyst in efficient electrolytic hydrogen production |
| CN112237932A (en) * | 2020-09-14 | 2021-01-19 | 青岛大学 | RuP3Modified two-dimensional CoP nanosheet hydrogen evolution electrocatalyst and preparation method and application thereof |
| CN112237932B (en) * | 2020-09-14 | 2023-05-05 | 青岛大学 | RuP 3 Modified two-dimensional CoP nanosheet hydrogen evolution electrocatalyst and preparation method and application thereof |
| CN112680741A (en) * | 2021-01-12 | 2021-04-20 | 江苏大学 | Preparation method and application of ruthenium-doped cobalt phosphide electrocatalyst |
| CN113668009A (en) * | 2021-07-15 | 2021-11-19 | 徐州天启新材料科技有限公司 | Hydrogen evolution reaction electrocatalyst of phosphide and preparation method |
| CN114293222A (en) * | 2021-11-22 | 2022-04-08 | 江西师范大学 | Synthesis method of ultrafine ruthenium diphosphide nanoparticle electrocatalyst |
| CN116014196A (en) * | 2022-12-07 | 2023-04-25 | 广东电网有限责任公司 | Photoelectric double-catalysis hydrogen evolution catalyst, preparation method thereof, membrane electrode and hydrogen fuel cell |
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