CN115961306A - Preparation method and application of a self-supporting porous sheet nickel phosphorus selenide electrode - Google Patents

Abstract

The invention provides a preparation method and application of a self-supporting porous flaky nickel selenide electrode. The preparation method of the material comprises the following steps: (1) Firstly, performing ultrasonic treatment on cut foam nickel in hydrochloric acid, ethanol and water for a plurality of times respectively to remove surface oxides, and then performing vacuum drying on the processed foam nickel; (2) Under the nitrogen atmosphere, red phosphorus is taken as a phosphorus source, selenium powder is taken as a selenium source, and the selenium powder, the red phosphorus and the processed foamed nickel are respectively placed in the upstream, the middle and the downstream of a tubular furnace for calcination. The material can be used as a bifunctional catalytic self-supporting porous flaky nickel selenide phosphor electrode, and shows excellent HER and OER bifunctional catalytic activity under alkaline conditions. The excellent electrochemical activity of NiPSe/NF is mainly attributed to the construction of a porous sheet self-supporting electrode and the synergistic effect between NiPx-NiSe 2. The method is simple to operate and convenient to implement, and can be popularized to the design and synthesis of a series of multifunctional composite materials with porous sheet structures and catalytic activity.

Description

Translated fromChinese

一种自支撑多孔片状磷硒化镍电极的制备方法及应用Preparation method and application of a self-supporting porous sheet-like nickel phospho-selenide electrode

技术领域Technical Field

本发明属于新型能源转化材料技术领域，更加具体地说，是一种将泡沫镍同时磷硒化而衍生的具有多孔片状结构的自支撑磷硒化镍电极的制备方法和在电催化水分解中的应用。The present invention belongs to the technical field of new energy conversion materials, and more specifically, is a method for preparing a self-supporting nickel phosphoselenide electrode having a porous sheet structure derived by simultaneously phosphoselenizing nickel foam, and its application in electrocatalytic water decomposition.

背景技术Background Art

相对于风能、太阳能、潮汐能等间歇能源，氢能作为最清洁的二次能源，能量密度高，清洁无污染，可作为未来最主要的能源之一。在众多制氢工艺中，电催化水裂解制氢气为生产可再生氢能提供了一种便捷、高效的新途径。电催化水解制氢，涉及阴极析氢反应(HER)和阳极析氧反应(OER)。然而HER和OER在动力学上都是缓慢的，需要高效的电催化剂来降低多步质子耦合电子过程的巨大能量障碍。目前商业应用的催化剂为贵金属Pt/C（HER）和RuO₂(OER)。然而，由于贵金属成本较高，限制其广泛应用。因此需要开发一种高效、稳定的非贵金属双功能电催化剂。Compared with intermittent energy sources such as wind energy, solar energy, and tidal energy, hydrogen energy is the cleanest secondary energy source with high energy density and clean and pollution-free. It can be used as one of the most important energy sources in the future. Among the many hydrogen production processes, electrocatalytic water splitting to produce hydrogen provides a convenient and efficient new way to produce renewable hydrogen energy. Electrocatalytic water splitting to produce hydrogen involves the cathode hydrogen evolution reaction (HER) and the anode oxygen evolution reaction (OER). However, both HER and OER are kinetically slow, and efficient electrocatalysts are required to reduce the huge energy barriers of the multi-step proton-coupled electron process. The catalysts currently used in commercial applications are precious metals Pt/C (HER) and RuO₂ (OER). However, the high cost of precious metals limits their widespread application. Therefore, it is necessary to develop an efficient and stable non-precious metal bifunctional electrocatalyst.

过渡金属磷化物由于具有高导电性、较高的本征活性等优点，一直受到人们关注。但其活性和稳定性仍不满足电解水的实际应用，因此许多研究者对过渡金属磷化物进行了进一步优化。例如，引入阴离子，改善过渡金属磷化物的电子结构。其中，由于硒原子电负性大于磷，当引入硒原子到过渡金属磷化物中，将有利于调节过渡金属磷化物的电子结构，改善材料表面吸附能，提高反应动能，从而进一步提高材料的电催化活性。此外，基于传统粉末状催化剂导电性差，易脱落等问题，合理设计自支撑电极是一种有效的解决方式。泡沫镍由于具有丰富的孔隙结构，导电性优异，且本身可做镍源，可作为一种极具潜力的自支撑导电基底。Transition metal phosphides have always attracted people's attention due to their advantages such as high conductivity and high intrinsic activity. However, their activity and stability still do not meet the practical application of water electrolysis, so many researchers have further optimized transition metal phosphides. For example, anions are introduced to improve the electronic structure of transition metal phosphides. Among them, since the electronegativity of selenium atoms is greater than that of phosphorus, when selenium atoms are introduced into transition metal phosphides, it will be beneficial to adjust the electronic structure of transition metal phosphides, improve the surface adsorption energy of materials, and increase the reaction kinetic energy, thereby further improving the electrocatalytic activity of materials. In addition, based on the problems of poor conductivity and easy shedding of traditional powdered catalysts, the rational design of self-supporting electrodes is an effective solution. Nickel foam can be used as a highly potential self-supporting conductive substrate because of its rich pore structure, excellent conductivity, and the fact that it can be used as a nickel source.

基于以上研究背景，设计一种简单易行的催化剂合成方法来制备 自支撑多孔片状磷硒化镍电极，来进一步降低电解水的实际电压，提高催化剂稳定性，具有非常重要的研究意义和应用价值。Based on the above research background, a simple and easy catalyst synthesis method is designed to prepare self-supporting porous sheet nickel phospho-selenide electrodes to further reduce the actual voltage of water electrolysis and improve the catalyst stability, which has very important research significance and application value.

发明内容Summary of the invention

本发明所要解决的技术问题是，针对传统电解水催化剂制备工艺复杂、效率低下等问题，提供一种一步磷硒化泡沫镍得到具有高效HER、OER双功能催化活性的多孔片状磷硒化镍自支撑电极的制备方法。本发明目的在于简单的一步磷硒化泡沫镍，得到自支撑多孔片状磷硒化镍电极，在碱性环境下展现出优异的HER、OER双功能催化活性，在大规模制备全水解电极具有广阔的应用前景。The technical problem to be solved by the present invention is to provide a method for preparing a porous sheet-like nickel phosphoselenide self-supporting electrode with high HER and OER bifunctional catalytic activity by one-step phosphoselenization of nickel foam, aiming at the problems of complex and low efficiency of the preparation process of traditional water electrolysis catalysts. The purpose of the present invention is to simply one-step phosphoselenization of nickel foam to obtain a self-supporting porous sheet-like nickel phosphoselenide electrode, which exhibits excellent HER and OER bifunctional catalytic activity in an alkaline environment and has broad application prospects in the large-scale preparation of full water splitting electrodes.

为实现上述技术目的，本发明提供了一种自支撑多孔片状磷硒化镍电极的制备方法，包括以下步骤：To achieve the above technical objectives, the present invention provides a method for preparing a self-supporting porous sheet-like nickel phospho-selenide electrode, comprising the following steps:

步骤一：先将剪裁好的泡沫镍（1*2㎠）在盐酸、乙醇、水中分别超声若干时间，随后将处理好的泡沫镍真空干燥。Step 1: First, ultrasonically treat the cut nickel foam (1*2㎠) in hydrochloric acid, ethanol, and water for a certain period of time, and then vacuum dry the treated nickel foam.

步骤二：在氮气气氛下，以红磷为磷源，硒粉为硒源，将硒粉、红磷和处理好的泡沫镍分别放在管式炉的上中下游，通过同步磷硒化反应得到自支撑多孔片状磷硒化镍电极（NiPSe/NF）。Step 2: Under nitrogen atmosphere, red phosphorus is used as the phosphorus source and selenium powder is used as the selenium source. Selenium powder, red phosphorus and treated nickel foam are placed in the upstream, middle and downstream of the tube furnace respectively, and a self-supporting porous sheet nickel phosphide selenide electrode (NiPSe/NF) is obtained through synchronous phosphoselenization reaction.

所述反应温度为400～600℃；硒粉和红磷的摩尔比为0:7，5:2，1:1，2:5，7:0。The reaction temperature is 400-600° C.; the molar ratio of selenium powder to red phosphorus is 0:7, 5:2, 1:1, 2:5, 7:0.

优选地，第二步中所述硒粉、红磷、泡沫镍在管式炉中的位置为上中下游。Preferably, in the second step, the selenium powder, red phosphorus and nickel foam are positioned at the upper, middle and lower reaches in the tube furnace.

优选地，第二步中所述硒粉和红磷的总摩尔数为7mmol。Preferably, the total molar number of the selenium powder and red phosphorus in the second step is 7 mmol.

优选地，第二步中所述硒粉和红磷的最优摩尔比为为2:5。Preferably, the optimal molar ratio of selenium powder to red phosphorus in the second step is 2:5.

优选地，第二步中所述升温速率为2℃

，第二步中所述在氮气的气氛下，泡沫镍与硒粉、红磷进行同步磷硒化反应，反应温度为400～600℃，反应时间为2h。Preferably, the heating rate in the second step is 2°C

In the second step, under a nitrogen atmosphere, nickel foam, selenium powder and red phosphorus undergo synchronous phosphoselenization reaction at a reaction temperature of 400-600° C. and a reaction time of 2 h.

优选地，所述磷硒化最优反应温度为500℃，反应时间为2h，在此优选条件下，同步磷硒化反应生成的催化电极材料的电催化活性更好，其催化电解水的效率也更高。Preferably, the optimal reaction temperature of the phosphoselenization is 500° C. and the reaction time is 2 h. Under this preferred condition, the catalytic electrode material generated by the synchronous phosphoselenization reaction has better electrocatalytic activity and higher efficiency in catalyzing the electrolysis of water.

所述的自支撑多孔片状磷硒化镍电极在双功能催化电极领域中的应用。The application of the self-supporting porous sheet-like nickel phospho-selenide electrode in the field of bifunctional catalytic electrodes.

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.我们设计一种简单方法将泡沫镍一步硒磷化得NiPSe/NF催化剂。1. We designed a simple method to selenophytate nickel foam in one step to obtain NiPSe/NF catalyst.

2.NiPSe/NF 作为双功能催化电极，得益于制备的材料具有多孔片状的形貌结构，以及NiPx-NiSe₂异质结构，有利于暴露更多的催化活性，增强NiPx-NiSe₂之间的协同作用。2. NiPSe/NF as a bifunctional catalytic electrode benefits from the porous flake-like morphology of the prepared material and the NiPx-_NiSe2 heterostructure, which is conducive to exposing more catalytic activity and enhancing the synergistic effect between NiPx-_NiSe2 .

3.该方法得到的产物作为HER、OER双功能催化电极比 RuO₂和Pt/C贵金属催化剂具有更好的催化性能，为提升非贵金属催化剂性能提供了参考。3. The product obtained by this method has better catalytic performance as a HER and OER bifunctional catalytic electrode than_RuO2 and Pt/C precious metal catalysts, providing a reference for improving the performance of non-precious metal catalysts.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为NiPSe-2-5-500的扫描电子显微镜图；FIG1 is a scanning electron microscope image of NiPSe-2-5-500;

图2为NiPSe-2-5-500的X粉末衍射图；FIG2 is an X-ray powder diffraction pattern of NiPSe-2-5-500;

图3为NF、NiSe、NiP、NiPSe-2-5-500、NiPSe-5-2-500、NiPSe-1-1-500、NiPSe-2-5-600、NiPSe-2-5-400的析氧极化曲线图；Fig. 3 is an oxygen evolution polarization curve diagram of NF, NiSe, NiP, NiPSe-2-5-500, NiPSe-5-2-500, NiPSe-1-1-500, NiPSe-2-5-600, and NiPSe-2-5-400;

图4为 NF、NiSe、NiP、NiPSe-2-5-500、NiPSe-5-2-500、NiPSe-1-1-500、NiPSe-2-5-600、NiPSe-2-5-400的析氢极化曲线图。Figure 4 is a diagram of the hydrogen evolution polarization curves of NF, NiSe, NiP, NiPSe-2-5-500, NiPSe-5-2-500, NiPSe-1-1-500, NiPSe-2-5-600, and NiPSe-2-5-400.

具体实施方式DETAILED DESCRIPTION

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 is further described below in conjunction with specific examples, but it should not be construed as limiting the present invention. If not specifically indicated, the technical means used in the examples 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 art.

实例1：Example 1:

自支撑多孔片状磷硒化镍电极及其制备方法，包括如下步骤：A self-supporting porous sheet-shaped nickel phospho-selenide electrode and a preparation method thereof, comprising the following steps:

A.将剪裁好的泡沫镍（1*2㎠）在 3M 盐酸、乙醇、水中分别超声 15 min，再将处理好的泡沫镍在 60℃下真空干燥。A. Ultrasonicate the cut nickel foam (1*2㎠) in 3M hydrochloric acid, ethanol and water for 15 min respectively, and then vacuum dry the treated nickel foam at 60℃.

B.以红磷作为磷源，硒粉作为硒源，称取红磷0.0584g、硒粉0.3803g，红磷和硒粉的总摩尔数为7mmol且红磷和硒粉的比例为2：5，将硒粉、红磷放在一个石英舟中，将步骤A中处理好的泡沫镍放在另一个石英舟中，将硒粉、红磷、泡沫镍分别放在管式炉的上中下游。在氮气的气氛下放在管式炉中进行煅烧。升温速率为2℃

，直至温度上升至500℃，并保温2h，自然冷却至室温，即可获得NiPSe-2-5-500电极材料。B. Use red phosphorus as the phosphorus source and selenium powder as the selenium source. Weigh 0.0584g of red phosphorus and 0.3803g of selenium powder. The total molar number of red phosphorus and selenium powder is 7mmol and the ratio of red phosphorus to selenium powder is 2:5. Put the selenium powder and red phosphorus in a quartz boat, put the nickel foam treated in step A in another quartz boat, and put the selenium powder, red phosphorus and nickel foam in the upper, middle and lower reaches of the tube furnace respectively. Calcine in a tube furnace under a nitrogen atmosphere. The heating rate is 2℃

, until the temperature rises to 500°C and is kept warm for 2 hours, and then naturally cooled to room temperature to obtain NiPSe-2-5-500 electrode material.

本实施例得到的NiPSe-2-5-500的扫描电子显微镜如图1所示。由图1可以看出：泡沫镍的表面经过同时磷硒化的过程，形成富含孔洞的平滑褶皱结构。The scanning electron microscope of NiPSe-2-5-500 obtained in this example is shown in Figure 1. As can be seen from Figure 1, the surface of the nickel foam forms a smooth wrinkled structure rich in pores after the simultaneous phosphorus-selenization process.

本实施例得到的NiPSe-2-5-500的X粉末衍射图如图2所示。由图2可以看出：所有衍射峰由NiSe₂、Ni₅P₄以及Ni₂P组成，表明成功合成了NiSe₂/Ni₅P₄/Ni₂P自支撑催化电极。The X-ray powder diffraction pattern of NiPSe-2-5-500 obtained in this example is shown in Figure 2. As can be seen from Figure 2, all diffraction peaks are composed of NiSe₂ , Ni₅ P₄ and Ni₂ P, indicating that the NiSe₂ /Ni₅ P₄ /Ni₂ P self-supporting catalytic electrode is successfully synthesized.

本实施例得到的NiPSe-2-5-500的电催化性能如图3和图4所示。由图3可以看出：在1M KOH中NiPSe-2-5-500在10mA cm^-2的电流密度下，析氧反应仅需要63mV的过电位；由图4可以看出：在10mA cm^-2的电流密度下，析氢反应仅需要163mV的过电位。与其他材料相比，NiPSe-2-5-500显示出最优异的OER、HER双功能催化活性，表明合适比例的磷硒化镍自支撑电极的构筑对催化活性的增强至关重要，不同组分间的协同作用有利于提高材料的催化活性。The electrocatalytic performance of NiPSe-2-5-500 obtained in this example is shown in Figures 3 and 4. As can be seen from Figure 3, the oxygen evolution reaction of NiPSe-2-5-500 in 1M KOH at a current density of 10mA cm^-2 only requires an overpotential of 63mV; as can be seen from Figure 4, the hydrogen evolution reaction at a current density of 10mA cm^-2 only requires an overpotential of 163mV. Compared with other materials, NiPSe-2-5-500 shows the best OER and HER bifunctional catalytic activity, indicating that the construction of a suitable proportion of nickel phosphoselenide self-supporting electrode is crucial to the enhancement of catalytic activity, and the synergistic effect between different components is conducive to improving the catalytic activity of the material.

实例2：Example 2:

A.将剪裁好的泡沫镍（1*2㎠）在3M盐酸、乙醇、水中分别超声15min，再将处理好的泡沫镍在60℃下真空干燥。A. Ultrasonicate the cut nickel foam (1*2㎠) in 3M hydrochloric acid, ethanol and water for 15 minutes respectively, and then vacuum dry the treated nickel foam at 60℃.

B.以红磷作为磷源，硒粉作为硒源，称取红磷0.1032g、硒粉0.2262g，红磷和硒粉的总摩尔数为7mmol且红磷和硒粉的比例为1：1，将硒粉、红磷放在一个石英舟中，将步骤A中处理好的泡沫镍放在另一个石英舟中，将硒粉、红磷、泡沫镍分别放在管式炉的上中下游，在氮气的气氛下放在管式炉中进行煅烧。升温速率为2℃

，直至温度上升至500℃，并保温2h，自然冷却至室温，即可获得NiPSe-1-1-500电极材料。B. Use red phosphorus as the phosphorus source and selenium powder as the selenium source, weigh 0.1032g of red phosphorus and 0.2262g of selenium powder, the total molar number of red phosphorus and selenium powder is 7mmol and the ratio of red phosphorus to selenium powder is 1:1, put the selenium powder and red phosphorus in a quartz boat, put the nickel foam treated in step A in another quartz boat, put the selenium powder, red phosphorus and nickel foam in the upper, middle and lower reaches of the tube furnace respectively, and calcine them in the tube furnace under nitrogen atmosphere. The heating rate is 2℃

, until the temperature rises to 500°C and is kept warm for 2 hours, and then naturally cooled to room temperature to obtain NiPSe-1-1-500 electrode material.

实例3：Example 3:

A.将剪裁好的泡沫镍（1*2㎠）在 3M 盐酸、乙醇、水中分别超声 15 min，再将处理好的泡沫镍在 60℃下真空干燥。A. Ultrasonicate the cut nickel foam (1*2㎠) in 3M hydrochloric acid, ethanol and water for 15 min respectively, and then vacuum dry the treated nickel foam at 60℃.

B.以红磷作为磷源，硒粉作为硒源，称取红磷0.1463g、硒粉0.1521g，红磷和硒粉的总摩尔数为7mmol且红磷和硒粉的比例为5：2，将硒粉、红磷放在一个石英舟中，将步骤A中处理好的泡沫镍放在另一个石英舟中，将硒粉、红磷、泡沫镍分别放在管式炉的上中下游，在氮气的气氛下放在管式炉中进行煅烧。升温速率为2℃

，直至温度上升至500℃，并保温2h，自然冷却至室温，即可获得NiPSe-5-2-500电极材料。B. Use red phosphorus as the phosphorus source and selenium powder as the selenium source, weigh 0.1463g of red phosphorus and 0.1521g of selenium powder, the total molar number of red phosphorus and selenium powder is 7mmol and the ratio of red phosphorus to selenium powder is 5:2, put the selenium powder and red phosphorus in a quartz boat, put the nickel foam treated in step A in another quartz boat, put the selenium powder, red phosphorus and nickel foam in the upper, middle and lower reaches of the tube furnace respectively, and calcine them in the tube furnace under nitrogen atmosphere. The heating rate is 2℃

, until the temperature rises to 500°C and is kept warm for 2 hours, and then naturally cooled to room temperature to obtain NiPSe-5-2-500 electrode material.

实例4：Example 4:

A.将剪裁好的泡沫镍（1*2㎠）在 3M 盐酸、乙醇、水中分别超声 15 min，再将处理好的泡沫镍在 60℃下真空干燥。A. Ultrasonicate the cut nickel foam (1*2㎠) in 3M hydrochloric acid, ethanol and water for 15 min respectively, and then vacuum dry the treated nickel foam at 60℃.

B.以红磷作为磷源，硒粉作为硒源，称取红磷0g、硒粉0.5326g，红磷和硒粉的总摩尔数为7mmol且红磷和硒粉的比例为0：7，将硒粉放在一个石英舟中，将步骤A中处理好的泡沫镍放在另一个石英舟中，将硒粉、泡沫镍分别放在管式炉的上下游，在氮气的气氛下放在管式炉中进行煅烧。升温速率为2℃

，直至温度上升至500℃，并保温2h，自然冷却至室温，即可获得NiSe电极材料。B. Use red phosphorus as the phosphorus source and selenium powder as the selenium source, weigh 0g of red phosphorus and 0.5326g of selenium powder, the total molar number of red phosphorus and selenium powder is 7mmol and the ratio of red phosphorus to selenium powder is 0:7, put the selenium powder in a quartz boat, put the nickel foam treated in step A in another quartz boat, put the selenium powder and nickel foam in the upstream and downstream of the tube furnace respectively, and calcine them in the tube furnace under nitrogen atmosphere. The heating rate is 2℃

, until the temperature rises to 500°C and is kept warm for 2 hours, and then naturally cooled to room temperature to obtain NiSe electrode material.

实例5：Example 5:

A.将剪裁好的泡沫镍（1*2㎠）在 3M 盐酸、乙醇、水中分别超声 15 min，再将处理好的泡沫镍在 60℃下真空干燥。A. Ultrasonicate the cut nickel foam (1*2㎠) in 3M hydrochloric acid, ethanol and water for 15 min respectively, and then vacuum dry the treated nickel foam at 60℃.

B.以红磷作为磷源，硒粉作为硒源，称取红磷0.2050g、硒粉0g，红磷和硒粉的总摩尔数为7mmol且红磷和硒粉的比例为7：0，将红磷放在一个石英舟中，将步骤A中处理好的泡沫镍放在另一个石英舟中，将红磷、泡沫镍分别放在管式炉的上下游，在氮气的气氛下放在管式炉中进行煅烧。升温速率为2℃

，直至温度上升至500℃，并保温2h，自然冷却至室温，即可获得NiP电极材料。B. Use red phosphorus as the phosphorus source and selenium powder as the selenium source, weigh 0.2050g of red phosphorus and 0g of selenium powder, the total molar number of red phosphorus and selenium powder is 7mmol and the ratio of red phosphorus to selenium powder is 7:0, put the red phosphorus in a quartz boat, put the nickel foam treated in step A in another quartz boat, put the red phosphorus and nickel foam in the upstream and downstream of the tube furnace respectively, and calcine them in the tube furnace under nitrogen atmosphere. The heating rate is 2℃

, until the temperature rises to 500℃ and keeps it for 2h, then naturally cools to room temperature to obtain NiP electrode material.

实例6：Example 6:

A.将剪裁好的泡沫镍（1*2㎠）在 3M 盐酸、乙醇、水中分别超声 15 min，再将处理好的泡沫镍在 60℃下真空干燥。A. Ultrasonicate the cut nickel foam (1*2㎠) in 3M hydrochloric acid, ethanol and water for 15 min respectively, and then vacuum dry the treated nickel foam at 60℃.

B.以红磷作为磷源，硒粉作为硒源，称取红磷0.0579g、硒粉0.3794g，红磷和硒粉的总摩尔数为7mmol且红磷和硒粉的比例为2：5，将硒粉、红磷放在一个石英舟中，将步骤A中处理好的泡沫镍放在另一个石英舟中，将硒粉、红磷、泡沫镍分别放在管式炉的上中下游，在氮气的气氛下放在管式炉中进行煅烧。升温速率为2℃

，直至温度上升至400℃，并保温2h，自然冷却至室温，即可获得NiPSe-5-2-400电极材料。B. Use red phosphorus as the phosphorus source and selenium powder as the selenium source, weigh 0.0579g of red phosphorus and 0.3794g of selenium powder, the total molar number of red phosphorus and selenium powder is 7mmol and the ratio of red phosphorus to selenium powder is 2:5, put the selenium powder and red phosphorus in a quartz boat, put the nickel foam treated in step A in another quartz boat, put the selenium powder, red phosphorus and nickel foam in the upper, middle and lower reaches of the tube furnace respectively, and calcine them in the tube furnace under nitrogen atmosphere. The heating rate is 2℃

, until the temperature rises to 400°C and is kept warm for 2 hours, and then naturally cooled to room temperature to obtain NiPSe-5-2-400 electrode material.

实例7：Example 7:

A.将剪裁好的泡沫镍（1*2㎠）在 3M 盐酸、乙醇、水中分别超声 15 min，再将处理好的泡沫镍在 60℃下真空干燥。A. Ultrasonicate the cut nickel foam (1*2㎠) in 3M hydrochloric acid, ethanol and water for 15 min respectively, and then vacuum dry the treated nickel foam at 60℃.

B.以红磷作为磷源，硒粉作为硒源，称取红磷0.0593g、硒粉0.3812g，红磷和硒粉的总摩尔数为7mmol且红磷和硒粉的比例为2：5，将硒粉、红磷放在一个石英舟中，将步骤A中处理好的泡沫镍放在另一个石英舟中，将硒粉、红磷、泡沫镍分别放在管式炉的上中下游，在氮气气氛下放在管式炉中进行煅烧。升温速率为2℃

，直至温度上升至600℃，并保温2h，自然冷却至室温，即可获得NiPSe-5-2-600电极材料。B. Use red phosphorus as the phosphorus source and selenium powder as the selenium source, weigh 0.0593g of red phosphorus and 0.3812g of selenium powder, the total molar number of red phosphorus and selenium powder is 7mmol and the ratio of red phosphorus to selenium powder is 2:5, put the selenium powder and red phosphorus in a quartz boat, put the nickel foam treated in step A in another quartz boat, put the selenium powder, red phosphorus and nickel foam in the upper, middle and lower reaches of the tube furnace respectively, and calcine them in the tube furnace under nitrogen atmosphere. The heating rate is 2℃

, until the temperature rises to 600°C and is kept warm for 2 hours, and then naturally cooled to room temperature to obtain NiPSe-5-2-600 electrode material.

Claims (10)

Translated fromChinese

1.自支撑多孔片状磷硒化镍电极的制备，包括如下步骤：1. The preparation of a self-supporting porous sheet-like nickel phosphoselenide electrode comprises the following steps:（1）先将剪裁好的泡沫镍（1*2㎠）在盐酸、乙醇、水中分别超声若干时间，随后将处理好的泡沫镍真空干燥。(1) First, the cut nickel foam (1*2㎠) was ultrasonically treated in hydrochloric acid, ethanol, and water for a certain period of time, and then the treated nickel foam was vacuum dried.2.（2）称取若干摩尔数的红磷、硒粉，将硒粉、红磷和处理好的泡沫镍放在氮气气氛下的管式炉中进行煅烧，得到自支撑磷硒化镍电极。2. (2) Weigh a certain number of moles of red phosphorus and selenium powder, place the selenium powder, red phosphorus and treated nickel foam in a tubular furnace under a nitrogen atmosphere and calcine them to obtain a self-supporting nickel phosphorus selenide electrode.3.所述反应温度为400～600℃；磷和硒的摩尔比为0:7，5:2，1:1，2:5，7:0。3. The reaction temperature is 400-600° C.; the molar ratio of phosphorus to selenium is 0:7, 5:2, 1:1, 2:5, 7:0.4.根据权利要求1所述的自支撑多孔片状磷硒化镍电极的制备方法，其特征在于，步骤一中的超声处理条件为：每次各超声15min。4. The method for preparing a self-supporting porous sheet-like nickel phosphoselenide electrode according to claim 1 is characterized in that the ultrasonic treatment conditions in step 1 are: each ultrasonic treatment lasts for 15 minutes.5.根据权利要求1所述的自支撑多孔片状磷硒化镍电极的制备方法，其特征在于，第二步中所述磷和硒的总摩尔数为7mmol，摩尔比为0:7，5:2，1:1，2:5，7:0。5. The method for preparing a self-supporting porous sheet-like nickel phosphoselenide electrode according to claim 1, characterized in that the total molar number of phosphorus and selenium in the second step is 7 mmol, and the molar ratio is 0:7, 5:2, 1:1, 2:5, 7:0.6.根据权利要求3所述的自支撑多孔片状磷硒化镍电极的制备方法，其特征在于，第二步中所述磷和硒的最优摩尔比为2:5。6. The method for preparing a self-supporting porous sheet-like nickel phosphorus selenide electrode according to claim 3, characterized in that the optimal molar ratio of phosphorus to selenium in the second step is 2:5.7.根据权利要求1所述的自支撑多孔片状磷硒化镍电极的制备方法，其特征在于，将硒粉、红磷、处理好的泡沫镍分别放在管式炉的上中下游进行煅烧。7. The method for preparing a self-supporting porous sheet-like nickel phospho-selenide electrode according to claim 1 is characterized in that selenium powder, red phosphorus, and treated nickel foam are placed in the upper, middle, and lower reaches of a tubular furnace for calcination.8.根据权利要求1所述的自支撑多孔片状磷硒化镍电极的制备方法，其特征在于，第三步中所述煅烧条件为：以 2℃

的速率升温至 500℃并保温120min，然后降至室温。8. The method for preparing a self-supporting porous sheet-like nickel phosphoselenide electrode according to claim 1, characterized in that the calcination conditions in the third step are:

The temperature was raised to 500 °C at a rate of 100 °C and kept at that temperature for 120 min, then dropped to room temperature.9.一种自支撑多孔片状磷硒化镍电极的制备方法，其特征在于，采用权利要求1～6任一项所述制备方法制得。9. A method for preparing a self-supporting porous sheet-like nickel phosphoselenide electrode, characterized in that it is prepared by the preparation method described in any one of claims 1 to 6.10.一种如权利要求7所述的自支撑多孔片状磷硒化镍复合材料作为电催化水分解反应电极的应用。10. Use of the self-supporting porous sheet-like nickel phospho-selenide composite material as claimed in claim 7 as an electrode for electrocatalytic water decomposition reaction.

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