CN114289043A - Preparation method and application of self-supporting porous nano-plate cobalt-nickel phosphide catalyst - Google Patents

Preparation method and application of self-supporting porous nano-plate cobalt-nickel phosphide catalyst Download PDF

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CN114289043A
CN114289043A CN202010999283.0A CN202010999283A CN114289043A CN 114289043 A CN114289043 A CN 114289043A CN 202010999283 A CN202010999283 A CN 202010999283A CN 114289043 A CN114289043 A CN 114289043A
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张丽
姜佳慧
王伟伟
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Xinjiang University
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Abstract

The invention provides a preparation method and application of a self-supporting porous nano-plate cobalt-nickel phosphide catalyst. The preparation method of the material comprises the following steps: (1) firstly, respectively carrying out ultrasonic treatment on cut foam nickel in hydrochloric acid, ethanol and water for a plurality of times, removing surface oxides, taking out and carrying out vacuum drying; (2) cobalt nitrate is used as metal salt, formic acid is used as ligand, methylamine is used as template, and metal formic acid frame is grown on foam nickel in situ uniformly by room temperature coprecipitation method; (3) sodium hypophosphite and a metal aururic acid frame growing in situ on the foamed nickel are placed at two ends of a quartz boat and placed in a tubular furnace for calcination by a low-temperature phosphorization method under the argon atmosphere by using the sodium hypophosphite to obtain the metal aururic acid frame growing in situ on the foamed nickelThe metal formic acid framework of (a) is derived from cobalt nickel phosphide of a porous nano-plate structure. The material can be used as a full-hydrolysis electrocatalyst and shows excellent HER, OER and full-hydrolysis performances under alkaline conditions. CoP-Ni5P4The excellent electrochemical performance of/NF is mainly attributed to the structure of the porous nano-plate, CoP and Ni5P4Synergistic effects between them and the stability of the self-supporting electrode. The method is simple to operate and convenient to implement, and can be popularized to design and synthesis of a series of composite materials with the advantage of structural multifunction.

Description

一种自支撑多孔纳米板钴镍磷化物催化剂制备方法及应用Preparation method and application of self-supporting porous nanoplate cobalt nickel phosphide catalyst

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,是一种自支撑多孔纳米板钴镍磷化物催化剂制备方法及应用。The invention belongs to the technical field of novel energy conversion materials, and more specifically relates to a preparation method and application of a self-supporting porous nano-plate cobalt nickel phosphide catalyst.

背景技术Background technique

如今,能源危机和环境问题已经受到全球的广泛关注,迫切需要发展能源转化和储备技术,用于生产清洁、可持续能源。氢能作为最清洁的二次能源,来源广泛,环境友好,可代替风能、太阳能、潮汐能等间歇能源成为未来最主要能源之一。对于大规模制氢,电催化水分解是一种高效可行的方法,其分为阳极的析氧反应和阴极的析氢反应,总的所需理论电压为1.23V。但由于阳极析氧反应缓慢的动力学,实际所需电压远高于理论电压,严重阻碍水分解的应用。因此,开发高效催化剂降低水分解的过电位。目前铂碳、氧化钌等贵金属被认为是最高效的析氢、析氧催化剂,但由于其原料稀缺、成本昂贵,稳定性差,限制其广泛应用,因此需要开发来源丰富、成本低廉,且稳定性好的过渡金属催化剂。Today, the energy crisis and environmental issues have attracted worldwide attention, and there is an urgent need to develop energy conversion and storage technologies for the production of clean and sustainable energy. As the cleanest secondary energy, hydrogen energy has a wide range of sources and is environmentally friendly. It can replace intermittent energy sources such as wind energy, solar energy and tidal energy and become one of the most important energy sources in the future. For large-scale hydrogen production, electrocatalytic water splitting is an efficient and feasible method, which is divided into an oxygen evolution reaction at the anode and a hydrogen evolution reaction at the cathode, and the total required theoretical voltage is 1.23 V. However, due to the slow kinetics of the oxygen evolution reaction at the anode, the actual required voltage is much higher than the theoretical voltage, which seriously hinders the application of water splitting. Therefore, developing efficient catalysts to reduce the overpotential of water splitting. At present, noble metals such as platinum carbon and ruthenium oxide are considered to be the most efficient catalysts for hydrogen evolution and oxygen evolution. However, due to the scarcity of raw materials, high cost and poor stability, their wide application is limited. Therefore, it is necessary to develop rich sources, low cost and good stability. of transition metal catalysts.

目前,制备电解水分解的催化剂材料有金属磷化物、硫化物、硒化物、氧化物、双氢氧化物等。皆通过调节材料的表面结构和电子结构来增强电催化剂的反应速率。其中,金属磷化物导电性较高,热稳定性、化学稳定性高,具有pH普适性,是用作析氢、析氧电催化剂良好的材料之一。近年来,金属有机框架由于本身形貌结构可调,孔隙丰富,化学性质活泼等优点,以其衍生的过渡金属磷化物受到广泛关注。然而,金属有机框架衍生磷化物,导电性较差,且通常为粉末状,用作电解水催化剂时,需要粘结剂将其附着到电极表面,随着析氢、析氧过程中气泡的产生,催化剂很容易脱落,从而会大大降低催化剂的稳定性。因此,为了提高金属有机框架衍生磷化物的导电性、稳定性和催化活性,减少粘结剂的使用,很多人采用了泡沫镍、碳纸、钛板等电流收集器作为催化剂生长基底。其中,泡沫镍具有大表面积、高导电性和稳定性,且本身可作为镍源,因此被认为是一种有前途的支撑基板。At present, the catalyst materials for the preparation of electrolytic water splitting include metal phosphides, sulfides, selenides, oxides, double hydroxides, and the like. All of them enhance the reaction rate of electrocatalysts by adjusting the surface structure and electronic structure of the material. Among them, metal phosphide has high electrical conductivity, high thermal stability and chemical stability, and has pH universality, and is one of the good materials used as electrocatalysts for hydrogen evolution and oxygen evolution. In recent years, metal-organic frameworks have attracted extensive attention due to their tunable morphology, abundant pores, and active chemical properties. However, metal-organic framework-derived phosphides have poor conductivity and are usually in powder form. When used as a catalyst for electrolysis of water, a binder is required to attach them to the electrode surface. With the generation of bubbles in the process of hydrogen evolution and oxygen evolution, The catalyst is easily detached, which greatly reduces the stability of the catalyst. Therefore, in order to improve the conductivity, stability and catalytic activity of metal-organic framework-derived phosphides and reduce the use of binders, many current collectors such as foamed nickel, carbon paper, and titanium plates are used as catalyst growth substrates. Among them, nickel foam has a large surface area, high electrical conductivity and stability, and can serve as a source of nickel by itself, so it is considered as a promising supporting substrate.

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一种自支撑多孔纳米板钴镍磷化物催化剂,来进一步降低全水解的实际电压,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, it is of great research significance to design a simple and easy catalyst synthesis method to prepare a self-supporting porous nanoplate cobalt-nickel phosphide catalyst to further reduce the actual voltage of full hydrolysis and improve the stability of the catalyst. and application value.

发明内容SUMMARY OF THE INVENTION

本发明所要解决的技术问题是,针对传统粉末状全水解催化剂存在的不足,提供一种自支撑多孔纳米板钴镍磷化物催化剂的简易制备方法及其在全水解中的应用。本发明得到的原位生长在泡沫镍上的金属有机框架衍生多孔纳米板钴镍磷化物催化剂,很好地继承了金属甲酸框架的形貌,利用磷化钴和四磷化五镍的协同作用,在碱性环境具有较低的全水解电位,较好的稳定性,在大规模制备全水解催化剂具有广阔的应用前景。The technical problem to be solved by the present invention is to provide a simple preparation method of a self-supporting porous nanoplate cobalt-nickel phosphide catalyst and its application in total hydrolysis, aiming at the shortcomings of traditional powdery perhydrolysis catalysts. The metal-organic framework-derived porous nano-plate cobalt-nickel phosphide catalyst obtained in-situ on the nickel foam obtained by the invention well inherits the morphology of the metal formate framework, and utilizes the synergistic effect of cobalt phosphide and penta-nickel tetraphosphide. , in an alkaline environment, it has a lower full hydrolysis potential and better stability, and has broad application prospects in the large-scale preparation of full hydrolysis catalysts.

为实现上述技术目的,本发明提供了一种自支撑多孔纳米板钴镍磷化物催化剂的制备方法,包括如下步骤:In order to achieve the above technical purpose, the present invention provides a preparation method of a self-supporting porous nanoplate cobalt nickel phosphide catalyst, comprising the following steps:

步骤一:先将剪裁好的泡沫镍(1*2cm2)在盐酸、乙醇、水中分别超声若干时间,去除表面氧化物及取出真空干燥。Step 1: First, sonicate the cut nickel foam (1*2cm 2 ) in hydrochloric acid, ethanol and water for several times to remove surface oxides and take out for vacuum drying.

步骤二:分别称取甲胺、甲酸,和六水合硝酸钴于25mL乙醇中搅拌均匀,得到配体溶液和金属盐溶液。将处理好的泡沫镍(1*2cm2)投入甲酸甲胺配体溶液中搅拌,再将搅拌均匀的金属盐溶液逐滴加入配体盐溶液中磁力搅拌、静置陈化若干时间,取出泡沫镍并用乙醇洗涤真空干燥,得到原位生长于泡沫镍的钴甲酸框架(Co-MFF/NF)。Step 2: respectively weigh methylamine, formic acid, and cobalt nitrate hexahydrate in 25 mL of ethanol and stir to obtain a ligand solution and a metal salt solution. Put the treated nickel foam (1*2cm 2 ) into the methylamine formate ligand solution and stir, and then add the uniformly stirred metal salt solution dropwise to the ligand salt solution with magnetic stirring, let it stand for some time, and take out the foam The nickel was washed with ethanol and dried in vacuo to obtain cobalt formate framework (Co-MFF/NF) grown in situ on nickel foam.

步骤三:通过低温磷化,将次亚磷酸钠与步骤二得到的前驱体放入石英舟两端置于管式炉中煅烧,得到磷化产物,即原位生长在泡沫镍上的金属甲酸框架衍生多孔纳米板结构的钴镍磷化物(CoP-Ni5P4/NF)。Step 3: By low-temperature phosphating, the sodium hypophosphite and the precursor obtained in step 2 are put into the quartz boat at both ends and placed in a tube furnace for calcination to obtain a phosphating product, that is, metal formic acid grown on foam nickel in situ Cobalt Nickel Phosphide (CoP-Ni 5 P 4 /NF) framework-derived porous nanoplate structure.

所述的金属、甲酸、甲胺的摩尔比为1:4~5:4~6。The molar ratio of the metal, formic acid and methylamine is 1:4~5:4~6.

优选地,第二步中所述金属和配体的摩尔比为1:4.5:4.5。Preferably, the molar ratio of the metal and the ligand in the second step is 1:4.5:4.5.

优选地,第二步中所述磁力搅拌时间为1小时。Preferably, the magnetic stirring time in the second step is 1 hour.

优选地,第二步中所述陈化时间为24小时。Preferably, the aging time in the second step is 24 hours.

优选地,第三步中所述煅烧温度为350℃。Preferably, the calcination temperature in the third step is 350°C.

优选的,第三步中所述前驱体:次亚磷酸钠质量比=1:10。Preferably, the mass ratio of the precursor in the third step: sodium hypophosphite=1:10.

所述的原位生长在泡沫镍上的金属甲酸框架衍生多孔纳米板结构的钴镍磷化物催化剂在电解水催化剂领域中的应用。The application of the cobalt-nickel phosphide catalyst of the metal formic acid framework-derived porous nano-plate structure grown on the foamed nickel in situ in the field of electrolysis water catalyst.

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金属甲酸框架原位生长于泡沫镍上,一步磷化得到多孔纳米板结构的CoP-Ni5P4/NF催化剂。1. We designed a simple method to in situ grow metal formate framework on nickel foam, and obtain CoP-Ni 5 P 4 /NF catalyst with porous nanoplate structure by one-step phosphating.

2. CoP-Ni5P4/NF作为全水解催化剂,得益于其多孔纳米板结构,以及CoP和Ni5P4/两相的相互作用,进一步提高全水解电催化性能。2. CoP-Ni 5 P 4 /NF acts as a perhydrolysis catalyst, benefiting from its porous nanoplate structure and the interaction of CoP and Ni 5 P 4 / two-phase, which further improves the electrocatalytic performance of per hydrolysis.

3.该方法得到的产物作为全解水电催化剂比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 an electrocatalyst for total water splitting than RuO 2 and Pt/C noble metal catalysts, which provides a reference for improving the performance of non-precious metal catalysts.

附图说明Description of drawings

图1为Co-MFF/NF,CoP-Ni5P4/NF的扫描图。Fig. 1 is the scanning diagram of Co-MFF/NF and CoP-Ni 5 P 4 /NF.

图2为CoP-Ni5P4/NF,CoP,Ni5P4/NF的X粉末衍射图。Figure 2 is the X-ray powder diffraction pattern of CoP-Ni 5 P 4 /NF, CoP, Ni 5 P 4 /NF.

图3为CoP-Ni5P4/NF、CoP+Ni5P4/NF、Ni5P4/NF、CoP、NF、RuO2(Pt/C)的析氧、 析氢极化曲线图,塔菲尔曲线,稳定性测试曲线。Figure 3 is the oxygen evolution and hydrogen evolution polarization curves of CoP-Ni 5 P 4 /NF, CoP+Ni 5 P 4 /NF, Ni 5 P 4 /NF, CoP, NF, RuO 2 (Pt/C), tower Phil Curve, Stability Test Curve.

图4为CoP-Ni5P4/NF║CoP-Ni5P4/NF的电催化全水解极化曲线图及稳定性测试曲线。Figure 4 shows the polarization curve and stability test curve of the electrocatalytic total hydrolysis of CoP-Ni 5 P 4 /NF║CoP-Ni 5 P 4 /NF.

具体实施方式Detailed ways

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 embodiments, but should not be construed as a limitation of the present invention. Unless otherwise specified, 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 technical field.

实例例1:Example Example 1:

自支撑多孔纳米板结构的钴镍磷化物催化剂其制备方法,包括如下步骤:The preparation method of the cobalt-nickel phosphide catalyst with self-supporting porous nanoplate structure comprises the following steps:

A.将剪裁好的泡沫镍(1*2cm2)在3M盐酸、乙醇、水中分别超声15分钟,去除泡沫镍表面氧化物,再将处理好的泡沫镍放入表面在60℃下真空干燥。A. The cut nickel foam (1*2cm 2 ) was sonicated in 3M hydrochloric acid, ethanol and water for 15 minutes to remove the oxide on the surface of the nickel foam, and then put the treated nickel foam on the surface and vacuum-dried at 60°C.

B.室温下,将六水合硝酸钴(1mmol)溶解至25ml乙醇中,再将甲酸水溶液(4.5mmol)、甲铵水溶液(4.5mmol)溶解至25ml乙醇中,将处理好的泡沫镍放入甲酸甲胺配体溶液中,分散均匀后将盐溶液逐滴滴加至配体溶液中,磁力搅拌1小时,静置24小时后用纯乙醇洗涤离心若干次,在60℃下真空干燥,得到原位均匀生长在泡沫镍的纳米板结构的钴甲酸框架(Co-MFF/NF),如图1a所示。B. At room temperature, dissolve cobalt nitrate hexahydrate (1 mmol) into 25 ml of ethanol, then dissolve formic acid aqueous solution (4.5 mmol) and methylammonium aqueous solution (4.5 mmol) into 25 ml of ethanol, and put the processed nickel foam into formic acid In the methylamine ligand solution, after uniform dispersion, the salt solution was added dropwise to the ligand solution, magnetically stirred for 1 hour, washed with pure ethanol and centrifuged several times after standing for 24 hours, and dried in vacuum at 60 °C to obtain the original solution. The cobalt formate framework (Co-MFF/NF) was uniformly grown on the nanoplate structure of nickel foam, as shown in Fig. 1a.

C.将步骤B中得到的Co-MFF/NF与次亚磷酸钠放入石英舟两端置于管式炉N2下350℃煅烧。其中,摩尔比Co-MFF/NF:次亚磷酸钠=1:10,得到原位均匀生长在泡沫镍上的金属甲酸框架衍生多孔纳米板结构的钴镍磷化物CoP-Ni5P4/NF,如图1b所示。C. Put the Co-MFF/NF and sodium hypophosphite obtained in step B into the quartz boat at both ends and place it in a tube furnace N 2 for calcination at 350°C. Among them, the molar ratio of Co-MFF/NF: sodium hypophosphite=1:10, the cobalt nickel phosphide CoP-Ni 5 P 4 /NF with metal formate framework-derived porous nanoplate structure uniformly grown in situ on nickel foam was obtained , as shown in Figure 1b.

本实施例得到的Co-MFF/NF的扫描电镜图如图1a所示。由图1a可以看出:200纳米厚的纳米片结构的钴甲酸框架经过室温沉淀法均匀的生长泡沫镍上。The scanning electron microscope image of Co-MFF/NF obtained in this example is shown in Figure 1a. It can be seen from Figure 1a that the cobalt formic acid framework with a nanosheet structure of 200 nm thick is uniformly grown on the nickel foam by the room temperature precipitation method.

本实施例得到的CoP-Ni5P4/NF的扫描电镜图如图1b所示。由图1b可以看出:磷化钴很好的继承钴甲酸框架的纳米板形貌,磷化过程由于配体分解纳米板表面变得粗糙多孔,泡沫镍表面经过磷化形成Ni5P4,从而变得粗糙。The scanning electron microscope image of CoP-Ni 5 P 4 /NF obtained in this example is shown in Fig. 1b. It can be seen from Figure 1b that cobalt phosphide well inherits the nanoplate morphology of the cobalt formate framework, the surface of the nanoplate becomes rough and porous due to the decomposition of ligands during the phosphating process, and the surface of the nickel foam is phosphated to form Ni 5 P 4 . thus become rough.

本实施例得到的CoP-Ni5P4/NF的X-射线粉末衍射如图2所示。由图2可以看出:除了三个明显的衍射峰为泡沫镍,还有一些小的衍射峰由钴甲酸框架衍生的CoP,和泡沫镍表面磷化形成的Ni5P4组成。The X-ray powder diffraction of CoP-Ni 5 P 4 /NF obtained in this example is shown in FIG. 2 . It can be seen from Figure 2 that in addition to the three obvious diffraction peaks for nickel foam, there are also some small diffraction peaks composed of CoP derived from cobalt formate framework and Ni 5 P 4 formed by phosphating on the surface of nickel foam.

本实施例得到的CoP-Ni5P4/NF的电催化性能如图4所示。由图4可以看出:在1M KOH中,CoP-Ni5P4/NF在50mA cm-2的电流密度下,析氧反应仅需要250mV的过电位,在10mA cm-2的电流密度下,析氢反应仅需要120mV的过电位。表明原位生长在泡沫镍上有利于电荷传递,催化剂活性位点的暴露,展现了优异的电催化性能。The electrocatalytic performance of the CoP-Ni 5 P 4 /NF obtained in this example is shown in FIG. 4 . It can be seen from Figure 4 that in 1M KOH, CoP-Ni 5 P 4 /NF at a current density of 50 mA cm -2 , the oxygen evolution reaction only requires an overpotential of 250 mV, and at a current density of 10 mA cm -2 , The hydrogen evolution reaction requires only an overpotential of 120 mV. It is shown that in situ growth on nickel foam is beneficial for charge transfer, exposure of catalyst active sites, and excellent electrocatalytic performance.

本实施例得到的CoP-Ni5P4/NF║CoP-Ni5P4/NF的电催化全水解极化曲线图及稳定性测试曲线如图4所示。由图4可以看出:在1M KOH中,CoP-Ni5P4/NF组成的两电极体系在10mA cm-2的电流密度下仅需要1.47V的电位,在50h的反应下,电流密度无明显衰减。表明CoP-Ni5P4/NF优异的全水解性能,超高的稳定性,具有良好的应用前景。The electrocatalytic total hydrolysis polarization curve and stability test curve of CoP-Ni 5 P 4 /NF║CoP-Ni 5 P 4 /NF obtained in this example are shown in FIG. 4 . It can be seen from Figure 4 that in 1M KOH, the two-electrode system composed of CoP-Ni 5 P 4 /NF only needs a potential of 1.47 V at a current density of 10 mA cm -2 , and the current density has no effect under the reaction of 50 h. significantly attenuated. It shows that CoP-Ni 5 P 4 /NF has excellent total hydrolysis performance, ultra-high stability, and has a good application prospect.

实例例2:Example Example 2:

A.室温下,将六水合硝酸钴(1mmol)溶解至25ml乙醇中,在将甲酸水溶液(4.5mmol)、甲铵水溶液(4.5mmol)溶解至25ml乙醇中,分散均匀后将盐溶液逐滴滴加至配体溶液中,磁力搅拌1小时,静置24小时后用纯乙醇洗涤离心若干次,在60℃下真空干燥,得到立方结构的Co-MFF。A. Dissolve cobalt nitrate hexahydrate (1 mmol) in 25 ml of ethanol at room temperature, dissolve formic acid aqueous solution (4.5 mmol) and methylammonium aqueous solution (4.5 mmol) into 25 ml of ethanol, disperse evenly, and add salt solution dropwise It was added to the ligand solution, stirred magnetically for 1 hour, washed with pure ethanol and centrifuged several times after standing for 24 hours, and vacuum-dried at 60 °C to obtain Co-MFF with cubic structure.

B.将步骤B中得到的Co-MFF与次亚磷酸钠放入石英舟两端置于管式炉中N2下350℃煅烧。其中,摩尔比Co-MFF:次亚磷酸钠=1:10,得到CoP。B. Put the Co-MFF and sodium hypophosphite obtained in step B into a quartz boat at both ends and place it in a tube furnace for calcination at 350°C under N 2 . Wherein, the molar ratio Co-MFF:sodium hypophosphite=1:10 to obtain CoP.

实例例3:Example Example 3:

A.将剪裁好的泡沫镍(1*2cm2)在3M盐酸、乙醇、水中分别超声15分钟,去除泡沫镍表面氧化物,再将处理好的泡沫镍放入表面在60℃下真空干燥。A. The cut nickel foam (1*2cm 2 ) was sonicated in 3M hydrochloric acid, ethanol and water for 15 minutes to remove the oxide on the surface of the nickel foam, and then put the treated nickel foam on the surface and vacuum-dried at 60°C.

B.将步骤A中得到的NF与次亚磷酸钠放入石英舟两端置于管式炉中N2下350℃煅烧。其中,摩尔比NF:次亚磷酸钠=1:10,得到Ni5P4/NF。B. Put the NF and sodium hypophosphite obtained in step A into a quartz boat and place both ends in a tube furnace for calcination at 350°C under N 2 . Wherein, the molar ratio NF:sodium hypophosphite=1:10 to obtain Ni 5 P 4 /NF.

Claims (6)

1.自支撑多孔纳米板钴镍磷化物催化剂,包括如下步骤:1. A self-supporting porous nanoplate cobalt nickel phosphide catalyst, comprising the following steps: (1)先将剪裁好的泡沫镍(1*2cm2)在盐酸、乙醇、水中分别超声若干时间,去除表面氧化物及取出真空干燥。(1) First, ultrasonically sonicate the cut nickel foam (1*2cm 2 ) in hydrochloric acid, ethanol and water for several times respectively to remove surface oxides and take out for vacuum drying. (2)分别称取甲胺、甲酸,和六水合硝酸钴于25mL乙醇中搅拌均匀,将处理好的泡沫镍(1*2cm2)投入甲酸甲胺配体溶液中搅拌,再将搅拌均匀的金属盐溶液逐滴加入配体盐溶液中磁力搅拌、静置陈化若干时间,取出泡沫镍并用乙醇洗涤真空干燥,得到原位均匀生长在泡沫镍的纳米板结构的钴甲酸框架。(2) respectively weighing methylamine, formic acid, and cobalt nitrate hexahydrate in 25 mL of ethanol and stirring uniformly, dropping the processed nickel foam (1*2 cm 2 ) into the methylamine formate ligand solution and stirring, and then stirring the uniformly stirred The metal salt solution was added dropwise to the ligand salt solution with magnetic stirring, left to age for several times, and the nickel foam was taken out and washed with ethanol and dried under vacuum to obtain a cobalt formate framework with a nanoplate structure uniformly grown on the nickel foam in situ. (3)称取次亚磷酸钠,将次亚磷酸钠与步骤二得到的前驱体放入石英舟两端置于管式炉中煅烧,得到磷化产物,即自支撑多孔纳米板钴镍磷化物催化剂。(3) take by weighing sodium hypophosphite, put the precursor obtained by sodium hypophosphite and step 2 into the quartz boat both ends and place it in a tube furnace for calcination to obtain a phosphating product, i.e. self-supporting porous nano-plate cobalt nickel phosphorus compound catalyst. 所述的金属、甲酸、甲胺的摩尔比为1:4~5:4~6。The molar ratio of the metal, formic acid and methylamine is 1:4-5:4-6. 2.根据权利要求1所述的自支撑多孔纳米板钴镍磷化物催化剂的制备方法,其特征在于,步骤一中的超声处理条件为:每次各超声15min。2 . The method for preparing a self-supporting porous nanoplate cobalt-nickel phosphide catalyst according to claim 1 , wherein the ultrasonic treatment conditions in step 1 are: each ultrasonic for 15 min. 3 . 3.根据权利要求2所述的自支撑多孔纳米板钴镍磷化物催化剂的制备方法,其特征在于,第二步中所述金属和配体的摩尔比为1:4.5:4.5。3 . The method for preparing a self-supporting porous nanoplate cobalt-nickel phosphide catalyst according to claim 2 , wherein the molar ratio of the metal and the ligand in the second step is 1:4.5:4.5. 4 . 4.根据权利要求2所述的自支撑多孔纳米板钴镍磷化物催化剂的制备方法,其特征在于,第二步中所述磁力搅拌时间为1小时,陈化时间为24小时,真空干燥温度为60℃。4. the preparation method of self-supporting porous nano-plate cobalt nickel phosphide catalyst according to claim 2, is characterized in that, described in the second step, the magnetic stirring time is 1 hour, and the aging time is 24 hours, and the vacuum drying temperature is 60°C. 5.根据权利要求3所述的自支撑多孔纳米板钴镍磷化物催化剂的制备方法,其特征在于,第三步中所述煅烧条件为:以2℃min-1的速度升温至350℃并保温120min,然后降至室温。5. The method for preparing a self-supporting porous nanoplate cobalt-nickel phosphide catalyst according to claim 3, wherein the calcination condition in the third step is: heating to 350°C at a speed of 2°C min -1 and Incubate for 120 min, then cool to room temperature. 6.根据权利要求3所述的自支撑多孔纳米板钴镍磷化物催化剂的制备方法,其特征在于,第三步中所述前驱体:次亚磷酸钠=1:10。6 . The method for preparing a self-supporting porous nanoplate cobalt-nickel phosphide catalyst according to claim 3 , wherein the precursor in the third step: sodium hypophosphite=1:10. 7 .
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