CN114892206A - Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof - Google Patents

Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof Download PDF

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CN114892206A
CN114892206A CN202210425361.5A CN202210425361A CN114892206A CN 114892206 A CN114892206 A CN 114892206A CN 202210425361 A CN202210425361 A CN 202210425361A CN 114892206 A CN114892206 A CN 114892206A
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蔡凤明
余芳
廖礼玲
李东阳
周海青
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Abstract

本发明提供了一种多元金属氮化物异质结纳米棒阵列复合电催化剂及其制备方法和应用，该复合电催化剂生长于泡沫镍导电基底上，包括MoO3‑x纳米棒以及生长于MoO3‑x纳米棒表面的Fe3N/Ni3N纳米颗粒；制备方法包括以下步骤：(1)采用水热反应在泡沫镍上生长NiMoO4纳米棒；在NiMoO4纳米棒上沉积铁基氧化物，得镍钼铁氧化物前驱体/泡沫镍复合材料；(2)将镍钼铁氧化物前驱体/泡沫镍复合材料进行热氨化处理，得到多元金属氮化物异质结纳米棒阵列电催化剂。本发明通过在NiMoO4纳米棒上沉积铁基氧化物、加热氨化处理，得到的异质结纳米棒阵列复合电催化剂在碱性海水等中表现出优异的OER和HER反应活性。

Figure 202210425361

The invention provides a multi-element metal nitride heterojunction nanorod array composite electrocatalyst and a preparation method and application thereof. The composite electrocatalyst is grown on a foamed nickel conductive substrate, and includes MoO 3-x nanorods and MoO 3 -x nanorods. Fe 3 N/Ni 3 N nanoparticles on the surface of ‑x nanorods; the preparation method includes the following steps: (1) using a hydrothermal reaction to grow NiMoO4 nanorods on nickel foam; depositing iron-based oxides on the NiMoO4 nanorods , to obtain nickel-molybdenum iron oxide precursor/foamed nickel composite material; (2) thermally ammoniating the nickel-molybdenum iron oxide precursor/foamed nickel composite material to obtain multi-element metal nitride heterojunction nanorod array electrocatalyst . In the present invention, by depositing iron-based oxides on NiMoO 4 nanorods and thermally ammoniated, the obtained heterojunction nanorod array composite electrocatalyst exhibits excellent OER and HER reactivity in alkaline seawater and the like.

Figure 202210425361

Description

一种多元金属氮化物异质结纳米棒阵列复合电催化剂及其制 备方法和应用A kind of multi-element metal nitride heterojunction nanorod array composite electrocatalyst and its preparation method and application

技术领域technical field

本发明属于电催化材料技术领域，尤其涉及一种多元金属氮化物异质结纳米棒阵列复合电催化剂及其制备方法和应用。The invention belongs to the technical field of electrocatalytic materials, and in particular relates to a composite electrocatalyst with a multi-element metal nitride heterojunction nanorod array and a preparation method and application thereof.

背景技术Background technique

对传统化石燃料的严重依赖给人类社会带来了迫在眉睫的能源和严重的环境问题。解决这一问题的一个很有前景的策略是电催化水裂解制氢，将电能储存在分子氢的化学键中。而且氢燃烧产物为水，无污染清洁，是未来可再生能源的重要组成部分。利用废热或可再生但间歇性的风能或太阳能发电亦可驱动水分解成，阴极析氢反应和阳极析氧反应。Heavy reliance on traditional fossil fuels brings imminent energy and serious environmental problems to human society. A promising strategy to address this problem is electrocatalytic water splitting to produce hydrogen, which stores electrical energy in the chemical bonds of molecular hydrogen. Moreover, the product of hydrogen combustion is water, which is non-polluting and clean, and is an important part of future renewable energy. The use of waste heat or renewable but intermittent wind or solar power can also drive water splitting, cathodic hydrogen evolution and anodic oxygen evolution.

无论酸性或碱性环境下，水的理论热力学分解电压均为1.23V。但实际上，需要比理论值高得多的电压，该差值称为过电位。因此，这两种反应都需要有效的电催化剂来降低过电位，电催化剂通过降低活化能来促进析氧反应(OER)或析氢反应(HER)缓慢的动力学，使在工业制氢上得到广泛应用。特别使双功能电催化剂，对两种反应都有活性，具有简化装置和降低成本的有点，更有利于实际应用。广泛用于实验室电解水研究的淡水在世界许多地方都是稀缺资源，如果大规模的电化学淡水分解将对重要的水资源造成沉重的压力。而海水是地球上最丰富的自然资源之一，占世界水资源总量的96.5％，几乎是取之不尽的资源。此外，电解海水有利于环境的净化。特别是对于干旱地区，还可以从海水中产生新鲜的饮用水。The theoretical thermodynamic decomposition voltage of water is 1.23V in either acidic or alkaline environment. In practice, however, a much higher voltage than the theoretical value is required, and this difference is called overpotential. Therefore, both reactions require efficient electrocatalysts to reduce the overpotential, and electrocatalysts promote the slow kinetics of the oxygen evolution reaction (OER) or hydrogen evolution reaction (HER) by reducing the activation energy, making them widely used in industrial hydrogen production. application. In particular, bifunctional electrocatalysts, which are active for both reactions, have the advantages of simplifying the device and reducing costs, and are more conducive to practical applications. Freshwater, widely used in laboratory water electrolysis research, is a scarce resource in many parts of the world, and large-scale electrochemical freshwater dissociation will put a heavy strain on important water resources. Seawater is one of the most abundant natural resources on earth, accounting for 96.5% of the world's total water resources, making it an almost inexhaustible resource. In addition, electrolysis of seawater is beneficial to the purification of the environment. Especially for dry areas, fresh drinking water can also be produced from seawater.

因此，开发高效的海水电解***用于大规模生产氢气是非常理想的，是可持续制氢和环境修复的革命性技术。然而，实现海水裂解仍具有三大挑战性。第一个挑战是由于海水中存在氯离子，会在阳极上发生氯的析氧反应(OER)与析氧反应构成竞争关系。而且碱性环境下的OER，氯将与OH-反应生成次氯酸盐所需电压比阳极OER高约480mV驱动500和1000mA/cm2大电流密度。第二个挑战是海水本质上的低导电性会导致缓慢的HER动力学。第三个挑战是海水具有很强的腐蚀性，海水中的非无害离子、细菌、微生物和小颗粒的存在，以及覆盖在催化剂表面的不溶性沉淀物(如氢氧化镁和氢氧化钙)的形成，这些都会可能毒害OER和HER催化剂并破坏其长期稳定性。由于这些棘手问题，目前关于海水裂解的双功能电催化剂的研究很少。Therefore, it is highly desirable to develop an efficient seawater electrolysis system for large-scale hydrogen production, which is a revolutionary technology for sustainable hydrogen production and environmental remediation. However, achieving seawater splitting still has three major challenges. The first challenge is that due to the presence of chloride ions in seawater, the oxygen evolution reaction (OER) of chlorine that occurs at the anode competes with the oxygen evolution reaction. Moreover, for OER in an alkaline environment, chlorine will react with OH - to generate hypochlorite, and the required voltage is about 480mV higher than that of anode OER to drive large current densities of 500 and 1000 mA/cm 2 . The second challenge is that the inherently low conductivity of seawater leads to slow HER kinetics. The third challenge is the highly corrosive nature of seawater, the presence of non-harmless ions, bacteria, microorganisms and small particles in seawater, as well as the presence of insoluble precipitates (such as magnesium hydroxide and calcium hydroxide) covering the catalyst surface. formation, which may poison OER and HER catalysts and disrupt their long-term stability. Due to these thorny issues, there are currently few studies on bifunctional electrocatalysts for seawater splitting.

因此，开发高性能、低成本和耐腐蚀强的双功能电催化剂用于大规模海水裂解具有重要意义。过渡金属氮化物(TMN)具有良好的耐腐蚀性能、导电性和机械强度，是电解海水裂解的理想材料。镍基材料是碱性电解槽中最常用的电催化剂。目前，基于镍、铁、钴等的金属氧化物表现出优异的电催化析氧性能。而基于镍、铁、钴等的金属合金在电催化析氢上具有优异的性能，如由于NiMo合金中的Ni位可以提供丰富的水解离中心，而Mo的加入可以优化合金表面的氢吸附，使NiMo合金具有优异的活性和稳定性，被广泛研究。而且近年来，有研究表明Ni3N/Ni、NiMoN和Ni-Fe-Mo三元合金在碱性淡水裂解具有高效的催化活性。Therefore, it is of great significance to develop bifunctional electrocatalysts with high performance, low cost and strong corrosion resistance for large-scale seawater cracking. Transition metal nitride (TMN) has good corrosion resistance, electrical conductivity and mechanical strength, and is an ideal material for electrolytic seawater cracking. Nickel-based materials are the most commonly used electrocatalysts in alkaline electrolyzers. Currently, metal oxides based on nickel, iron, cobalt, etc. exhibit excellent electrocatalytic oxygen evolution performance. And metal alloys based on nickel, iron, cobalt, etc. have excellent performance in electrocatalytic hydrogen evolution. For example, because the Ni sites in NiMo alloy can provide abundant water dissociation centers, and the addition of Mo can optimize the hydrogen adsorption on the surface of the alloy, making the NiMo alloys have been widely studied due to their excellent activity and stability. And in recent years, studies have shown that Ni 3 N/Ni, NiMoN and Ni-Fe-Mo ternary alloys have high catalytic activity in alkaline fresh water cracking.

发明内容SUMMARY OF THE INVENTION

本发明所要解决的技术问题是，克服以上背景技术中提到的不足和缺陷，提供一种多元金属氮化物异质结纳米棒阵列复合电催化剂及其制备方法和应用，本发明通过在NiMoO4纳米棒上沉积铁基氧化物、加热氨化处理，得到的异质结纳米棒阵列复合电催化剂在碱性海水等中表现出优异的OER和HER反应活性。The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the above background technology, and provide a multi-element metal nitride heterojunction nanorod array composite electrocatalyst and its preparation method and application . Deposition of iron-based oxides on the nanorods, heating and ammoniation treatment, the obtained heterojunction nanorod array composite electrocatalysts showed excellent OER and HER reactivity in alkaline seawater and so on.

为解决上述技术问题，本发明提出的技术方案为：In order to solve the above-mentioned technical problems, the technical scheme proposed by the present invention is:

一种多元金属氮化物异质结纳米棒阵列复合电催化剂的制备方法，包括以下步骤：A preparation method of a multi-element metal nitride heterojunction nanorod array composite electrocatalyst, comprising the following steps:

(1)采用水热反应在泡沫镍上生长NiMoO4纳米棒；在NiMoO4纳米棒上沉积铁基氧化物，得镍钼铁氧化物前驱体/泡沫镍复合材料；(1) using hydrothermal reaction to grow NiMoO4 nanorods on nickel foam; depositing iron-based oxides on NiMoO4 nanorods to obtain nickel molybdenum iron oxide precursor/foamed nickel composite material;

(2)将所述镍钼铁氧化物前驱体/泡沫镍复合材料进行热氨化处理，得到多元金属氮化物异质结纳米棒阵列电催化剂。(2) subjecting the nickel molybdenum iron oxide precursor/foamed nickel composite material to thermal ammoniation treatment to obtain a multi-element metal nitride heterojunction nanorod array electrocatalyst.

上述制备方法中，步骤(1)中，采用水热反应在泡沫镍上生长NiMoO4纳米棒具体包括以下步骤：将0.04mol/L的镍盐和0.01mol/L的钼盐溶解于水中，得溶液；将所述溶液装入高压釜中，再将泡沫镍浸入溶液中，进行水热反应，水热温度为150℃，反应时间为8h，然后冷却至室温，取出泡沫镍后经干燥，得到生长有NiMoO4纳米棒的泡沫镍。In the above preparation method, in step (1), using hydrothermal reaction to grow NiMoO nanorods on nickel foam specifically includes the following steps: dissolving 0.04mol/L nickel salt and 0.01mol/L molybdenum salt in water to obtain solution; put the solution into an autoclave, and then immerse the nickel foam in the solution to carry out a hydrothermal reaction, the hydrothermal temperature is 150 ° C, and the reaction time is 8 h, then cooled to room temperature, and the nickel foam is taken out and dried to obtain Nickel foam grown with NiMoO4 nanorods.

步骤(1)中镍钼铁氧化物前驱体/泡沫镍复合材料的条件具体如下：将铁盐溶解于溶剂，溶剂为H2O、DMF、C2H5OH中的一种或几种中，制备得到前驱体溶液，前驱体溶液中铁盐的浓度为0.02～0.2g/mL；再用前驱体溶液在生长有NiMoO4纳米棒的泡沫镍表面上可控沉积铁基氧化物，进行晾干，得镍钼铁氧化物前驱体/泡沫镍复合材料。The conditions of the nickel-molybdenum-iron oxide precursor/foamed nickel composite material in step (1) are as follows: the iron salt is dissolved in a solvent, and the solvent is one or more of H 2 O, DMF, and C 2 H 5 OH. , a precursor solution was prepared, and the concentration of iron salt in the precursor solution was 0.02-0.2 g/mL; then the precursor solution was used to controllably deposit iron-based oxides on the surface of the nickel foam with NiMoO 4 nanorods grown, and air-dried , to obtain nickel molybdenum iron oxide precursor/foam nickel composite material.

上述制备方法中，步骤(2)中的热氨化处理的条件为：以氨气作为氮源，氩气作为保护气，升温至300～550℃，恒温2～6h；恒温烧结束，停止通入氨气，在氩气保护下随炉冷却至室温，得到多元金属氮化物异质结纳米棒阵列复合电催化剂。In the above preparation method, the conditions of the thermal ammoniation treatment in step (2) are as follows: using ammonia as the nitrogen source and argon as the protective gas, the temperature is raised to 300-550 ° C, and the constant temperature is 2-6 h; Ammonia gas is introduced, and the furnace is cooled to room temperature under the protection of argon gas to obtain a composite electrocatalyst with a multi-element metal nitride heterojunction nanorod array.

通过上述条件的加热氮化处理，可利于进一步提升异质结纳米棒阵列复合电催化剂的催化性能。The thermal nitridation treatment under the above conditions can be beneficial to further improve the catalytic performance of the heterojunction nanorod array composite electrocatalyst.

作为一个总的发明构思，本发明提供了一种多元金属氮化物异质结纳米棒阵列复合电催化剂，其由上述制备方法制备而成，其生长于泡沫镍导电基底上，化学组成表示为Fe3N/Ni3N/MoO3-x(x＝0,1)，包括MoO3-x(x＝0,1)纳米棒以及生长于MoO3-x(x＝0,1)纳米棒表面的Fe3N/Ni3N纳米颗粒。其中MoO3-x(x＝0,1)表示由MoO2和MoO3组成。As a general inventive concept, the present invention provides a multi-element metal nitride heterojunction nanorod array composite electrocatalyst, which is prepared by the above preparation method, grown on a foam nickel conductive substrate, and its chemical composition is expressed as Fe 3 N/Ni 3 N/MoO 3-x (x=0,1), including MoO 3-x (x=0,1) nanorods and growing on the surface of MoO 3-x (x=0,1) nanorods Fe 3 N/Ni 3 N nanoparticles. Wherein MoO 3-x (x=0,1) means it is composed of MoO 2 and MoO 3 .

作为一个总的发明构思，本发明提供了一种上述制备方法制备得到的多元金属氮化物异质结纳米棒阵列复合电催化剂或上述多元金属氮化物异质结纳米棒阵列复合电催化剂在在水电解制氢或水电解制氧中的应用。As a general inventive concept, the present invention provides a multi-element metal nitride heterojunction nanorod array composite electrocatalyst prepared by the above preparation method or the above multi-element metal nitride heterojunction nanorod array composite electrocatalyst in water Application in hydrogen production by electrolysis or oxygen production by water electrolysis.

优选的，所述水电解制氢、水电解制氧中的水包括碱性水、碱性海水、中性水中任意一种。Preferably, the water in the water electrolysis for hydrogen production and water electrolysis for oxygen production includes any one of alkaline water, alkaline seawater and neutral water.

与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:

1、本发明制备了一种基于泡沫镍的多元金属氮化物异质结纳米棒阵列复合电催化剂，制备过程简单、操作条件温和和氮化过程易于控制。本发明制备的异质结纳米棒阵列复合电催化剂除了具有高效的碱性水析氧和析氢催化功能外，在碱性海水中也表现出卓越的析氧和析氢性能，其能够同时实现高效的碱性海水析氧和析氢，大幅度降低了碱性海水电解过程的能耗，实现了大电流高效制氢。其构建全解器件在大电流密度500mA/cm2和1000mA/cm2下能长达100小时的稳定性操作，这在国际上甚少有报道。本发明解决了同时高效海水析氧、析氢和长期稳定性的难题，对大规模海水制氢具有重要意义。1. The present invention prepares a multi-element metal nitride heterojunction nanorod array composite electrocatalyst based on foamed nickel, and the preparation process is simple, the operating conditions are mild, and the nitridation process is easy to control. The heterojunction nanorod array composite electrocatalyst prepared by the present invention not only has high-efficiency oxygen evolution and hydrogen evolution catalytic functions in alkaline water, but also exhibits excellent oxygen evolution and hydrogen evolution performance in alkaline seawater, and can simultaneously realize high-efficiency oxygen evolution and hydrogen evolution. The oxygen and hydrogen evolution of alkaline seawater greatly reduces the energy consumption of the alkaline seawater electrolysis process and realizes high-current and high-efficiency hydrogen production. The fully decomposed device constructed by it can operate stably for up to 100 hours at high current densities of 500 mA/cm 2 and 1000 mA/cm 2 , which is rarely reported internationally. The present invention solves the problems of simultaneous high-efficiency seawater oxygen evolution, hydrogen evolution and long-term stability, and has great significance for large-scale seawater hydrogen production.

2、本发明以廉价的NiMoO4纳米棒作为前驱体，制备得到的复合材料上的电催化剂Fe3N/Ni3N/MoO3-x(x＝0,1)具有多级孔隙度结构，能够提供大量的活性位点、高效的电荷转移和快速的气体产物释放，耐腐蚀性强，使复合电催化剂具有高效的反应活性。2. The present invention uses cheap NiMoO 4 nanorods as precursors, and the electrocatalyst Fe 3 N/Ni 3 N/MoO 3-x (x=0,1) on the prepared composite material has a multi-level porosity structure, It can provide a large number of active sites, efficient charge transfer and rapid gas product release, and has strong corrosion resistance, making the composite electrocatalyst have efficient reactivity.

3、本发明的多元金属氮化物异质结纳米棒阵列复合电催化剂在碱性介质中仅需要280mV和36mV的过电位可驱动500mA/cm2电流密度的析氧和析氢，而在碱性海水中只需要311mV和29mV的过电位可提供500mA/cm2电流密度的析氧和析氢，对于提高碱性海水电解制氢效率以及大规模推广碱性海水裂解具有重要意义。3. The multi-element metal nitride heterojunction nanorod array composite electrocatalyst of the present invention only needs an overpotential of 280mV and 36mV to drive oxygen evolution and hydrogen evolution with a current density of 500mA/ cm2 in an alkaline medium. Only 311mV and 29mV overpotentials are required to provide oxygen evolution and hydrogen evolution with a current density of 500mA/ cm2 , which is of great significance for improving the hydrogen production efficiency of alkaline seawater electrolysis and the large-scale promotion of alkaline seawater cracking.

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，下面描述中的附图是本发明的一些实施例，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，还可以根据这些附图获得其他的附图。In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are For some embodiments of the present invention, for those of ordinary skill in the art, other drawings can also be obtained according to these drawings without creative efforts.

图1为实施例1中异质结纳米棒阵列复合电催化剂的不同放大倍数的SEM图；Fig. 1 is the SEM images of different magnifications of the heterojunction nanorod array composite electrocatalyst in Example 1;

图2为实施例1中异质结纳米棒阵列复合电催化剂局部的TEM图；2 is a partial TEM image of the heterojunction nanorod array composite electrocatalyst in Example 1;

图3为实施例1中异质结纳米棒阵列复合电催化剂Fe3N/Ni3N/MoO3-x的XRD图；3 is the XRD pattern of the heterojunction nanorod array composite electrocatalyst Fe 3 N/Ni 3 N/MoO 3-x in Example 1;

图4为最初以及1000个循环后实施例1中异质结纳米棒阵列复合电催化剂在碱性1MKOH溶液中析氧反应的电流-电位极化曲线图；Figure 4 is a current-potential polarization curve of the oxygen evolution reaction of the heterojunction nanorod array composite electrocatalyst in an alkaline 1MKOH solution initially and after 1000 cycles;

图5为实施例1中异质结纳米棒阵列复合电催化剂在1M KOH溶液中进行电催化析氧反应的稳定性测试曲线图；5 is a graph showing the stability test of the electrocatalytic oxygen evolution reaction of the heterojunction nanorod array composite electrocatalyst in Example 1 in a 1M KOH solution;

图6为最初以及1000个循环后实施例1中异质结纳米棒阵列复合电催化剂在碱性1MKOH溶液中析氢反应的电流-电位极化曲线图；Fig. 6 is a current-potential polarization curve of the hydrogen evolution reaction of the heterojunction nanorod array composite electrocatalyst in an alkaline 1MKOH solution initially and after 1000 cycles;

图7为实施例1中异质结纳米棒阵列复合电催化剂在碱性1M KOH溶液中进行电催化析氢反应的稳定性测试曲线图；7 is a graph showing the stability test of the electrocatalytic hydrogen evolution reaction of the heterojunction nanorod array composite electrocatalyst in an alkaline 1M KOH solution in Example 1;

图8为实施例1中异质结纳米棒阵列复合电催化剂在碱性1M KOH海水溶液中析氧反应的电流-电位极化曲线图；Fig. 8 is the current-potential polarization curve of the oxygen evolution reaction of the heterojunction nanorod array composite electrocatalyst in alkaline 1M KOH seawater solution in Example 1;

图9为实施例1中异质结纳米棒阵列复合电催化剂在碱性1M KOH海水溶液中析氧反应的稳定性测试曲线图；9 is a graph showing the stability test of the oxygen evolution reaction of the heterojunction nanorod array composite electrocatalyst in an alkaline 1M KOH seawater solution in Example 1;

图10为实施例1中异质结纳米棒阵列复合电催化剂在碱性1M KOH海水溶液中析氢反应的电流-电位极化曲线图；10 is a current-potential polarization curve diagram of the hydrogen evolution reaction of the heterojunction nanorod array composite electrocatalyst in an alkaline 1M KOH seawater solution in Example 1;

图11为实施例1中异质结纳米棒阵列复合电催化剂在碱性1M KOH海水溶液中析氢反应的稳定性测试曲线图；Fig. 11 is a graph showing the stability test of the hydrogen evolution reaction of the heterojunction nanorod array composite electrocatalyst in an alkaline 1M KOH seawater solution in Example 1;

图12为实施例1中异质结纳米棒阵列复合电催化剂在碱性1M KOH溶液以及在1MKOH海水溶液全解的LSV曲线图；Fig. 12 is the LSV curve diagram of the complete solution of the heterojunction nanorod array composite electrocatalyst in alkaline 1M KOH solution and in 1MKOH seawater solution in Example 1;

图13为实施例1中异质结纳米棒阵列复合电催化剂在碱性1M KOH溶液中全水解的稳定性测试曲线图；13 is a graph showing the stability test of the total hydrolysis of the heterojunction nanorod array composite electrocatalyst in an alkaline 1M KOH solution in Example 1;

图14为实施例1中异质结纳米棒阵列复合电催化剂在碱性1M KOH海水溶液中全水解的稳定性测试曲线图；14 is a graph showing the stability test of the total hydrolysis of the heterojunction nanorod array composite electrocatalyst in an alkaline 1M KOH seawater solution in Example 1;

图15为异质结纳米棒阵列复合电催化剂Fe3N/Ni3N/MoO3-x和NiMoN电催化剂在碱性1MKOH溶液中析氧反应的电流极化曲线对比图；Figure 15 is a comparison diagram of the current polarization curves of the heterojunction nanorod array composite electrocatalyst Fe 3 N/Ni 3 N/MoO 3-x and NiMoN electrocatalyst in the oxygen evolution reaction in alkaline 1MKOH solution;

图16为异质结纳米棒阵列复合电催化剂Fe3N/Ni3N/MoO3-x和NiMoN电催化剂在碱性1MKOH海水溶液中析氧反应的电流极化曲线对比图；Figure 16 is a comparison diagram of the current polarization curves of the heterojunction nanorod array composite electrocatalyst Fe 3 N/Ni 3 N/MoO 3-x and NiMoN electrocatalyst in the oxygen evolution reaction in alkaline 1MKOH seawater solution;

图17为异质结纳米棒阵列复合电催化剂Fe3N/Ni3N/MoO3-x和NiMoN电催化剂在碱性1MKOH溶液中析氢反应的电流极化曲线对比图；Figure 17 is a comparison diagram of the current polarization curves of the hydrogen evolution reaction of the heterojunction nanorod array composite electrocatalyst Fe 3 N/Ni 3 N/MoO 3-x and NiMoN electrocatalyst in alkaline 1MKOH solution;

图18为异质结纳米棒阵列复合电催化剂Fe3N/Ni3N/MoO3-x和NiMoN电催化剂在碱性1MKOH海水溶液中析氢反应的电流极化曲线对比图。Figure 18 is a comparison diagram of the current polarization curves of the heterojunction nanorod array composite electrocatalyst Fe 3 N/Ni 3 N/MoO 3-x and NiMoN electrocatalyst in the hydrogen evolution reaction in alkaline 1MKOH seawater solution.

具体实施方式Detailed ways

为了便于理解本发明，下文将结合说明书附图和较佳的实施例对本发明做更全面、细致地描述，但本发明的保护范围并不限于以下具体实施例。In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and in detail below with reference to the accompanying drawings and preferred embodiments of the specification, but the protection scope of the present invention is not limited to the following specific embodiments.

除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。Unless otherwise defined, all technical terms used hereinafter have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments, and are not intended to limit the protection scope of the present invention.

除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or can be prepared by existing methods.

实施例1：Example 1:

一种多元金属氮化物异质结纳米棒阵列复合电催化剂的制备方法，包括以下步骤：A preparation method of a multi-element metal nitride heterojunction nanorod array composite electrocatalyst, comprising the following steps:

步骤(1)：step 1):

制备生长有NiMoO4纳米棒的泡沫镍：将Ni(NO3)2·6H2O和(NH4)6Mo7O24·4H2O溶解于水中，得溶液，溶液中Ni(NO3)2·6H2O的浓度为0.04mol/L，(NH4)6Mo7O24·4H2O的浓度为0.01mol/L；将上述溶液装入高压釜中，再将一片泡沫镍(4cm长*4cm宽)浸入溶液中，将高压釜置于烘箱中，加热到150℃，并加热8h，冷却至室温，取出泡沫镍，放在通风橱晾干，得生长有NiMoO4纳米棒的泡沫镍。Preparation of nickel foam with NiMoO 4 nanorods: Dissolving Ni(NO 3 ) 2 ·6H 2 O and (NH 4 ) 6 Mo 7 O 24 ·4H 2 O in water to obtain a solution, in which Ni(NO 3 ) The concentration of 2.6H2O is 0.04mol /L, and the concentration of ( NH4 ) 6Mo7O24.4H2O is 0.01mol /L ; length * 4cm width) immersed in the solution, placed the autoclave in an oven, heated to 150 ° C, and heated for 8 hours, cooled to room temperature, took out the nickel foam, and placed it in a fume hood to dry, to obtain a foam with NiMoO4 nanorods grown. nickel.

步骤(2)：Step (2):

制备镍钼铁氧化物前驱体/泡沫镍复合材料：将一定量的Fe(NO3)3·9H2O充分溶解于溶剂中，溶剂DMF，制备得到前驱体溶液，前驱体溶液中上述铁盐的浓度为0.15g/mL；然后用前驱体溶液在步骤(1)中的生长有NiMoO4纳米棒的泡沫镍表面上可控沉积铁基氧化物，进行晾干，得到镍钼铁氧化物前驱体/泡沫镍复合材料。Preparation of nickel molybdenum iron oxide precursor/foamed nickel composite material: a certain amount of Fe(NO 3 ) 3 9H 2 O is fully dissolved in a solvent, and the solvent is DMF to prepare a precursor solution. The above iron salt in the precursor solution is prepared. The concentration of 0.15g/mL; then use the precursor solution to controllably deposit iron-based oxides on the surface of the nickel foam with NiMoO4 nanorods grown in step (1), and dry them to obtain nickel-molybdenum-iron oxide precursors Body/foam nickel composite.

步骤(3)：Step (3):

将经步骤(2)得到的镍钼铁氧化物前驱体/泡沫镍复合材料放在管式炉温区中心进行加热氨化处理，以氨气作为氮源，惰性气体氩气作为保护气，将管式炉中心温度设置为450℃，恒温5h；恒温烧结束，停止通入氨气，在氩气保护下(氩气的气流量可小于10sccm)随炉冷却至室温，即可得到多元金属氮化物异质结纳米棒阵列复合电催化剂Fe3N/Ni3N/MoO3-x。The nickel-molybdenum-iron oxide precursor/foamed nickel composite material obtained in step (2) is placed in the center of the tubular furnace temperature zone for heating and ammoniation treatment, using ammonia gas as a nitrogen source and inert gas argon gas as a protective gas, and The central temperature of the tube furnace is set to 450°C, and the constant temperature is 5h; after the constant temperature firing, the feeding of ammonia gas is stopped. Compound heterojunction nanorod array composite electrocatalyst Fe 3 N/Ni 3 N/MoO 3-x .

将上述步骤得到的异质结纳米棒阵列复合电催化剂Fe3N/Ni3N/MoO3-x进行不同溶液环境的OER，HER反应以及配全解器件进行全解水电解。The heterojunction nanorod array composite electrocatalyst Fe 3 N/Ni 3 N/MoO 3-x obtained in the above steps was subjected to OER and HER reactions in different solution environments, and was equipped with a total solution device for total water electrolysis.

多元金属氮化物异质结纳米棒阵列复合电催化剂的SEM图和局部TEM图，如图1和图2所示；表征(Fe3N/Ni3N/MoO3-x(x＝0,1))晶体结构和组分的X射线衍射图如图3所示。SEM images and partial TEM images of the multi-element metal nitride heterojunction nanorod array composite electrocatalyst, as shown in Figure 1 and Figure 2; Characterization (Fe 3 N/Ni 3 N/MoO 3-x (x=0,1 )) The X-ray diffraction pattern of the crystal structure and composition is shown in Figure 3.

上述异质结纳米棒阵列复合电催化剂以泡沫镍为基底，泡沫镍上生长有MoO3-x纳米棒。通过SEM图可看到，Fe3N/Ni3N纳米颗粒生长于MoO3-x纳米棒上，可显示出大的表面积，暴露出大量活性位点，加快电子的转移速度，有助于提高催化性能的电催化剂。而TEM图能够进一步证实纳米颗粒均匀分布在纳米棒上。通过XRD图可看到电催化剂由Fe3N、Ni3N和MoO3-x(x＝0,1)组成。The above heterojunction nanorod array composite electrocatalyst is based on foamed nickel, and MoO 3-x nanorods are grown on the foamed nickel. It can be seen from the SEM image that the Fe 3 N/Ni 3 N nanoparticles grow on the MoO 3-x nanorods, which can show a large surface area, expose a large number of active sites, accelerate the electron transfer speed, and help improve the Electrocatalysts with catalytic properties. The TEM images can further confirm that the nanoparticles are uniformly distributed on the nanorods. It can be seen from the XRD pattern that the electrocatalyst is composed of Fe 3 N, Ni 3 N and MoO 3-x (x=0,1).

对比例1：Comparative Example 1:

NiMoN电催化剂的制备方法，包括以下步骤：The preparation method of NiMoN electrocatalyst comprises the following steps:

步骤(1)：step 1):

制备生长有NiMoO4的泡沫镍：将0.04mol/L的Ni(NO3)2·6H2O和0.01mol/L(NH4)6Mo7O24·4H2O溶解于水中，得溶液；将上述溶液装入高压釜中，再将一片泡沫镍(4cm长*4cm宽)浸入溶液中,将高压釜置于烘箱中，加热到150℃，并加热8h，冷却至室温，取出泡沫镍，放在通风橱晾干，得生长有NiMoO4的泡沫镍。Preparation of nickel foam grown with NiMoO 4 : dissolve 0.04mol/L Ni(NO 3 ) 2 ·6H 2 O and 0.01mol/L (NH 4 ) 6 Mo 7 O 24 ·4H 2 O in water to obtain a solution; Put the above solution into an autoclave, then immerse a piece of nickel foam (4cm long * 4cm wide) into the solution, place the autoclave in an oven, heat it to 150°C, heat it for 8h, cool it to room temperature, take out the nickel foam, Put it in a fume hood to dry, and have NiMoO 4 grown nickel foam.

步骤(2)：Step (2):

将经步骤(1)得到的生长有NiMoO4的泡沫镍放在管式炉温区中心进行加热氨处理，以氨气作为氮源，惰性气体氩气作为保护气，将管式炉中心温度设置为450℃，恒温5h；恒温烧结束，停止通入氨气，在氩气保护下随炉冷却至室温，可得到NiMoN电催化剂。 The nickel foam with NiMoO obtained in step (1) is placed in the center of the tubular furnace temperature zone for heating ammonia treatment, using ammonia gas as the nitrogen source, and inert gas argon as the protective gas, and the center temperature of the tubular furnace is set. The temperature is 450 °C, and the constant temperature is 5 h; when the constant temperature burning is completed, the feeding of ammonia gas is stopped, and the NiMoN electrocatalyst can be obtained by cooling to room temperature with the furnace under the protection of argon gas.

性能测试：Performance Testing:

将实施例1中制备得到的多元金属氮化物异质结纳米棒阵列复合电催化剂(异质结纳米棒阵列复合电催化剂)进行下述性能测试：The following performance tests were performed on the multi-element metal nitride heterojunction nanorod array composite electrocatalyst (heterojunction nanorod array composite electrocatalyst) prepared in Example 1:

1、将异质结纳米棒阵列复合电催化剂应用于1M KOH环境的电催化析氧反应。1. The heterojunction nanorod array composite electrocatalyst was applied to the electrocatalytic oxygen evolution reaction in 1M KOH environment.

电催化析氧性能主要使用美国知名品牌GAMRYRefrence 3000电化学工作站，采用标准的三电极体系(工作电极、对电极、参比电极)测试。其中异质结纳米棒阵列复合电催化剂作为工作电极，Hg/HgO电极为参比电极，石墨纸为对电极，以1M KOH溶液为电解质溶液，析氧的电化学测试的结果如图4和图5所示。The electrocatalytic oxygen evolution performance was mainly tested by using a well-known American brand GAMRYRefrence 3000 electrochemical workstation, using a standard three-electrode system (working electrode, counter electrode, reference electrode). The heterojunction nanorod array composite electrocatalyst is used as the working electrode, the Hg/HgO electrode is the reference electrode, the graphite paper is the counter electrode, and the 1M KOH solution is used as the electrolyte solution. 5 shown.

图4为最初以及1000个循环后异质结纳米棒阵列复合电催化剂在碱性1M KOH溶液中析氧反应的电流-电位极化曲线图；图5为异质结纳米棒阵列复合电催化剂在1M KOH溶液中进行电催化析氧反应的稳定性测试曲线图。通过图4，5可看出复合电催化剂具有优异的析氧催化性能和耐久的稳定性操作，仅需要280mV的过电位可驱动500电流密度，且在50mA/cm2和500mA/cm2电流密度下保持60小时左右的耐久性操作。Figure 4 shows the current-potential polarization curves of the heterojunction nanorod array composite electrocatalyst in the oxygen evolution reaction in alkaline 1M KOH solution initially and after 1000 cycles; Figure 5 shows the heterojunction nanorod array composite electrocatalyst in the Stability test curve of electrocatalytic oxygen evolution reaction in 1M KOH solution. From Figures 4 and 5, it can be seen that the composite electrocatalyst has excellent oxygen evolution catalytic performance and durable stable operation. It only needs an overpotential of 280mV to drive a current density of 500, and the current density is 50mA/ cm2 and 500mA/ cm2 . It maintains a durable operation of about 60 hours.

2、将异质结纳米棒阵列复合电催化剂应用于1M KOH环境的电催化析氢反应。2. The heterojunction nanorod array composite electrocatalyst was applied to the electrocatalytic hydrogen evolution reaction in 1M KOH environment.

电化学析氢性能主要使用美国品牌GAMRYReference 3000电化学工作站，采用标准的三电极体系进行测试，其中异质结纳米棒阵列复合电催化剂为工作电极，Hg/HgO电极为参比电极，石墨纸为对电极，电解液主要是1M KOH溶液。析氢的电化学测试结果如图6和图7所示。The electrochemical hydrogen evolution performance is mainly tested by the American brand GAMRYReference 3000 electrochemical workstation, and the standard three-electrode system is used for testing, in which the heterojunction nanorod array composite electrocatalyst is the working electrode, the Hg/HgO electrode is the reference electrode, and the graphite paper is the counter electrode. Electrode, the electrolyte is mainly 1M KOH solution. The electrochemical test results of hydrogen evolution are shown in Figures 6 and 7.

图6为最初以及1000个循环后异质结纳米棒阵列复合电催化剂在碱性1M KOH溶液中析氢反应的电流-电位极化曲线图。图7为复合电催化剂在碱性1M KOH溶液中进行电催化析氢反应的稳定性测试曲线图。图6，7显示出催化剂具有优异的析氢催化性能和耐久的稳定性操作，仅需要36mV的过电位可驱动500电流密度，且在-50mA/cm2和-500mA/cm2电流密度下保持60小时左右的耐久性操作。Figure 6 shows the current-potential polarization curves for the hydrogen evolution reaction of the heterojunction nanorod array composite electrocatalyst in alkaline 1M KOH solution initially and after 1000 cycles. Figure 7 is a graph showing the stability test of the composite electrocatalyst in the electrocatalytic hydrogen evolution reaction in alkaline 1M KOH solution. Figures 6, 7 show that the catalysts have excellent hydrogen evolution catalytic performance and durable stable operation, only an overpotential of 36mV is required to drive 500 current densities, and it maintains 60 current densities at -50mA/ cm2 and -500mA/ cm2 current densities Hours of durable operation.

3、将异质结纳米棒阵列复合电催化剂应用于1M KOH海水(1M KOH seawater)环境的电催化析氧反应。3. The heterojunction nanorod array composite electrocatalyst was applied to the electrocatalytic oxygen evolution reaction in 1M KOH seawater environment.

电化学析氧性能主要使用美国品牌GAMRYReference 3000电化学工作站，采用标准的三电极体系进行测试，其中异质结纳米棒阵列复合电催化剂为工作电极，Hg/HgO电极为参比电极，石墨纸为对电极，电解液主要是1M KOH海水溶液。析氧的电化学测试结果如图8和图9所示。The electrochemical oxygen evolution performance was mainly tested by the American brand GAMRYReference 3000 electrochemical workstation, and the standard three-electrode system was used for testing, in which the heterojunction nanorod array composite electrocatalyst was the working electrode, the Hg/HgO electrode was the reference electrode, and the graphite paper was the working electrode. For the counter electrode, the electrolyte is mainly 1M KOH seawater solution. The electrochemical test results of oxygen evolution are shown in Figures 8 and 9.

图8为异质结纳米棒阵列复合电催化剂在碱性1M KOH海水溶液中析氧反应的电流-电位极化曲线图。图9为异质结纳米棒阵列复合电催化剂在碱性1M KOH海水溶液中析氧反应的稳定性测试曲线图。通过图8，9可看出复合电催化剂具有优异的析氧催化性能和耐久的稳定性操作，仅需要311mV的过电位可驱动500电流密度，且在300mA/cm2和500mA/cm2电流密度下保持40小时左右的耐久性操作。Figure 8 is a current-potential polarization curve of the heterojunction nanorod array composite electrocatalyst for the oxygen evolution reaction in alkaline 1M KOH seawater solution. Figure 9 is a graph showing the stability test curve of the heterojunction nanorod array composite electrocatalyst in the oxygen evolution reaction in alkaline 1M KOH seawater solution. From Figures 8 and 9, it can be seen that the composite electrocatalyst has excellent oxygen evolution catalytic performance and durable stable operation. It only needs an overpotential of 311mV to drive a current density of 500, and the current density is 300mA/ cm2 and 500mA/ cm2 . It maintains a durable operation of about 40 hours.

4、将异质结纳米棒阵列复合电催化剂的制备及其应用于1M KOH海水环境的电催化析氢反应。4. Preparation of heterojunction nanorod array composite electrocatalyst and its application in electrocatalytic hydrogen evolution reaction in 1M KOH seawater environment.

电化学析氢性能主要使用美国品牌GAMRYReference 3000电化学工作站，采用标准的三电极体系进行测试，其中异质结纳米棒阵列复合电催化剂为工作电极，Hg/HgO电极为参比电极，石墨纸为对电极，电解液主要是1M KOH海水溶液。析氢的电化学测试结果如图10和图11所示。The electrochemical hydrogen evolution performance is mainly tested by the American brand GAMRYReference 3000 electrochemical workstation, and the standard three-electrode system is used for testing, in which the heterojunction nanorod array composite electrocatalyst is the working electrode, the Hg/HgO electrode is the reference electrode, and the graphite paper is the counter electrode. Electrode, the electrolyte is mainly 1M KOH seawater solution. The electrochemical test results of hydrogen evolution are shown in Figure 10 and Figure 11.

图10为异质结纳米棒阵列复合电催化剂在碱性1M KOH海水溶液中析氢反应的电流-电位极化曲线图。图11为异质结纳米棒阵列复合电催化剂在碱性1M KOH海水溶液中析氢反应的稳定性测试曲线图。图10，11显示出催化剂具有优异的析氢催化性能和耐久的稳定性操作，仅需要29mV的过电位可驱动500电流密度，且在-300mA/cm2和-500mA/cm2电流密度下保持40小时左右的耐久性操作。Figure 10 is the current-potential polarization curve of the heterojunction nanorod array composite electrocatalyst in the hydrogen evolution reaction in alkaline 1M KOH seawater solution. Figure 11 is a graph showing the stability test curve of the heterojunction nanorod array composite electrocatalyst in the hydrogen evolution reaction in alkaline 1M KOH seawater solution. Figures 10, 11 show that the catalyst has excellent hydrogen evolution catalytic performance and durable stable operation, requiring only 29mV overpotential to drive 500 current densities, and maintain 40 current densities at -300mA/ cm2 and -500mA/ cm2 current densities Hours of durable operation.

5、将异质结纳米棒阵列复合电催化剂应用于1M KOH以及1M KOH海水环境的全解反应。5. The heterojunction nanorod array composite electrocatalyst was applied to the total decomposition reaction of 1M KOH and 1M KOH seawater environment.

电化学析氢性能主要使用美国品牌GAMRYReference 3000电化学工作站，采用标准的两电极体系进行测试，其中异质结纳米棒阵列复合电催化剂为阳极和阴极工作电极，电解液主要是1M KOH溶液和1M KOH海水溶液。全解的测试结果如图12，图13和图14所示。The electrochemical hydrogen evolution performance is mainly tested by the American brand GAMRYReference 3000 electrochemical workstation, and the standard two-electrode system is used for testing, in which the heterojunction nanorod array composite electrocatalyst is the anode and cathode working electrodes, and the electrolytes are mainly 1M KOH solution and 1M KOH Sea water solution. The test results of the full solution are shown in Figure 12, Figure 13 and Figure 14.

图12为异质结纳米棒阵列复合电催化剂在碱性1M KOH溶液以及在1M KOH海水溶液全解的LSV曲线图。图13为异质结纳米棒阵列复合电催化剂在碱性1M KOH溶液中全水解的稳定性测试曲线图。图14为异质结纳米棒阵列复合电催化剂在碱性1M KOH海水溶液中全水解的稳定性测试曲线图。Figure 12 shows the LSV curves of the total dissociation of the heterojunction nanorod array composite electrocatalyst in alkaline 1M KOH solution and in 1M KOH seawater solution. Figure 13 is a graph showing the stability test curve of the heterojunction nanorod array composite electrocatalyst in total hydrolysis in alkaline 1M KOH solution. Figure 14 is a graph showing the stability test curve of the heterojunction nanorod array composite electrocatalyst in total hydrolysis in alkaline 1M KOH seawater solution.

由图13-14可知，用此催化剂分别作为阳极和阴极构建两电极全解器件时，在1MKOH溶液中，仅需要1.577V和1.617V可分别驱动大电流密度500mA/cm2和1000mA/cm2的反应，而在1M KOH海水溶液中只需要1.599V和1.658V即可驱动大电流密度500mA/cm2和1000mA/cm2的海水分解，这比目前国际上报道的全解器件都要好。It can be seen from Figure 13-14 that when this catalyst is used as the anode and cathode to construct a two-electrode total decomposition device, in 1MKOH solution, only 1.577V and 1.617V are needed to drive large current densities of 500mA/cm 2 and 1000mA/cm 2 , respectively. However, in 1M KOH seawater solution, only 1.599V and 1.658V are required to drive seawater decomposition at large current densities of 500mA/ cm2 and 1000mA/ cm2 , which is better than the currently reported fully decomposed devices.

6、将异质结纳米棒阵列复合电催化剂与对比例1中没引入Fe离子通过相同条件处理得到的NiMoN电催化剂在1M KOH溶液和1M KOH海水溶液中进行析氧和析氢反应。6. The heterojunction nanorod array composite electrocatalyst and the NiMoN electrocatalyst obtained by the same conditions without introducing Fe ions in Comparative Example 1 were subjected to oxygen evolution and hydrogen evolution reactions in 1M KOH solution and 1M KOH seawater solution.

电催化性能主要使用美国知名品牌GAMRYRefrence 3000电化学工作站，采用标准的三电极体系(工作电极、对电极、参比电极)测试。其中异质结纳米棒阵列复合电催化剂和NiMoN电催化剂作为工作电极，Hg/HgO电极为参比电极，石墨纸为对电极，以1M KOH和1MKOH海水溶液为电解质溶液，电化学测试的结果如图15、图16、图17图18所示，其中，图15、图16、图17图18中，异质结纳米棒阵列复合电催化剂对应Fe3N/Ni3N/MoO3-x，NiMoN对应NiMoN电催化剂。从图中可以看到通过引入Fe离子的异质结纳米棒阵列复合电催化剂在碱性1M KOH溶液和1M KOH海水溶液都可以显著提高催化剂的活性。The electrocatalytic performance was mainly measured using a well-known American brand GAMRYRefrence 3000 electrochemical workstation, using a standard three-electrode system (working electrode, counter electrode, reference electrode). The heterojunction nanorod array composite electrocatalyst and NiMoN electrocatalyst are used as the working electrode, the Hg/HgO electrode is the reference electrode, the graphite paper is the counter electrode, and 1M KOH and 1MKOH seawater solution is used as the electrolyte solution. The electrochemical test results are as follows As shown in Figure 15, Figure 16, Figure 17, Figure 18, wherein, in Figure 15, Figure 16, Figure 17, and Figure 18, the heterojunction nanorod array composite electrocatalyst corresponds to Fe 3 N/Ni 3 N/MoO 3-x , NiMoN corresponds to NiMoN electrocatalyst. It can be seen from the figure that by introducing Fe ions into the heterojunction nanorod array composite electrocatalyst, the activity of the catalyst can be significantly improved in both alkaline 1M KOH solution and 1M KOH seawater solution.

Claims (9)

1. A preparation method of a multi-metal nitride heterojunction nanorod array composite electrocatalyst is characterized by comprising the following steps of:
(1) NiMoO growth on foamed nickel by hydrothermal reaction 4 A nanorod; in NiMoO 4 Depositing iron-based oxide on the nano-rods to obtain a nickel-molybdenum iron oxide precursor/foamed nickel composite material;
(2) and carrying out thermal amination treatment on the nickel-molybdenum-iron oxide precursor/foamed nickel composite material to obtain the multi-metal nitride heterojunction nanorod array electrocatalyst.
2. The method according to claim 1, wherein in the step (1), NiMoO is grown on the nickel foam by hydrothermal reaction 4 The nanorod specifically comprises the following steps: dissolving nickel salt and molybdenum salt in water to obtain solution; putting the solution into a high-pressure kettle, soaking foam nickel into the solution, performing hydrothermal reaction, cooling to room temperature, taking out the foam nickel, and drying to obtain the NiMoO grown 4 Foamed nickel of nanorods.
3. The method according to claim 2, wherein the concentration of the nickel salt in the solution is 0.04mol/L, and the concentration of the molybdenum salt is 0.01 mol/L; the temperature of the hydrothermal reaction is 150 ℃, and the reaction time is 4-10 h.
4. The method according to claim 1, wherein step (1) comprises the steps of: dissolving iron salt in solvent to obtain precursorA bulk solution; then using precursor solution to grow NiMoO 4 The iron-based oxide is controllably deposited on the surface of the foamed nickel of the nanorod, and then the nanorod is dried to obtain the nickel-molybdenum-iron oxide precursor/foamed nickel composite material.
5. The method according to claim 4, wherein the solvent is H 2 O、DMF、C 2 H 5 One or more of OH; the concentration of the ferric salt in the precursor solution is 0.02-0.2 g/mL.
6. The production method according to any one of claims 2 to 5, wherein the thermal amination is performed under the following conditions: heating to 300-550 ℃ by taking ammonia gas as a nitrogen source and argon gas as protective gas, and keeping the temperature for 2-6 h; and stopping introducing ammonia gas after constant-temperature burning is finished, and cooling to room temperature along with the furnace under the protection of argon gas to obtain the multi-metal nitride heterojunction nanorod array composite electrocatalyst.
7. A multi-metal nitride heterojunction nanorod array composite electrocatalyst prepared by the method of any one of claims 1 to 6, grown on a foamed nickel conductive substrate, comprising MoO 3-x (x ═ 0,1) nanorods and growth on MoO 3-x (x ═ 0,1) Fe on nanorod surface 3 N/Ni 3 And N nano-particles.
8. The application of the multi-metal nitride heterojunction nanorod array composite electrocatalyst prepared by the preparation method of any one of claims 1-6 or the multi-metal nitride heterojunction nanorod array composite electrocatalyst of claim 7 in water electrolysis hydrogen production or water electrolysis oxygen production.
9. The use of claim 8, wherein the water in the water electrolysis hydrogen production and the water electrolysis oxygen production comprises any one of alkaline water, alkaline seawater and neutral water.
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