CN106694005A - Preparation method of electric catalyst for acidic fully-decomposed water - Google Patents

Preparation method of electric catalyst for acidic fully-decomposed water Download PDF

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CN106694005A
CN106694005A CN201611081350.0A CN201611081350A CN106694005A CN 106694005 A CN106694005 A CN 106694005A CN 201611081350 A CN201611081350 A CN 201611081350A CN 106694005 A CN106694005 A CN 106694005A
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manganese
cobalt
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章立寒
刘熙俊
罗俊
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Tianjin University of Technology
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

本发明公开了一种酸性全分解水电催化剂的制备方法，先对导电基底超声清洗，再配制具有可溶性钴盐、可溶性锰盐、氟化铵和尿素的第一水溶液，于反应釜中，在基底表面上垂直生长锰钴碱式碳酸盐纳米线阵列；再配置具有可溶性钴盐、可溶性锰盐、还原剂、氟化铵和尿素的第二水溶液，再进行二次生长锰钴碱式碳酸盐纳米片，形成锰钴碱式碳酸盐纳米片复合纳米线多级结构；再于管式炉中，以次磷酸钠或磷酸钠为磷源，于氮气或氩气气氛中，在200～1000℃煅烧，制得掺锰的磷化钴超薄纳米片复合纳米线多级结构的酸性全分解水电催化剂。本发明通过简单的水热合成和低温磷化处理过程，工艺简单，易于调控，是一种极具应用前景的酸性全分解水中极好的双功能电催化剂。

The invention discloses a preparation method of an acidic full decomposition water electrocatalyst. Firstly, the conductive base is ultrasonically cleaned, and then the first aqueous solution with soluble cobalt salt, soluble manganese salt, ammonium fluoride and urea is prepared, and the first aqueous solution is placed in a reaction kettle on the base Manganese-cobalt basic carbonate nanowire arrays are grown vertically on the surface; then a second aqueous solution with soluble cobalt salt, soluble manganese salt, reducing agent, ammonium fluoride and urea is configured, and then secondary growth of manganese-cobalt basic carbonate is carried out Salt nanosheets to form a multi-level structure of manganese-cobalt basic carbonate nanosheets composite nanowires; then in a tube furnace, using sodium hypophosphite or sodium phosphate as a phosphorus source, in a nitrogen or argon atmosphere, at 200 ~ Calcined at 1000°C, the manganese-doped cobalt phosphide ultra-thin nanosheet composite nanowire hierarchical structure acidic total decomposition hydroelectric catalyst was prepared. The invention adopts simple hydrothermal synthesis and low-temperature phosphating treatment process, has simple process and is easy to control, and is an excellent bifunctional electrocatalyst with great application prospects for fully decomposing acidic water.

Description

一种酸性全分解水电催化剂的制备方法A kind of preparation method of acidic total water decomposition electrocatalyst

技术领域technical field

本发明是关于电催化剂的，特别涉及一种过渡金属掺杂的具有超薄纳米片复合纳米线多级结构阵列的酸性全分解水电催化剂及其制备方法。The invention relates to an electrocatalyst, in particular to a transition metal-doped acidic total water decomposition electrocatalyst with an ultra-thin nanosheet composite nanowire multilevel structure array and a preparation method thereof.

背景技术Background technique

在同一种电解质中的全电解水产氢和产氧是应对能源短缺和环境污染的一种有效解决途径，但同时也面临着巨大的挑战。在这个领域中，设计和获得高性能的析氢反应(HER)和析氧反应(OER)双功能电催化电极材料一直是研究人员的目标。目前，贵金属(Pt，IrO2和RuO2等)催化剂表面活性高，对HER和OER有极好的催化性能，但是其成本高、储量少并不能满足实际需求。因此，近年来发展以过渡金属元素组成的碳化物、氯化物、硫化物和磷化物等作为高效环保的HER催化剂，过渡金属元素组成的氧化物和磷酸盐等作为高效OER电催化剂成为当前的研究热点。但是，这些催化剂在同一电解质中同时用作OER和HER双功能催化剂，则存在着活性低、稳定性差等问题，从而限制了它们的规模化应用。基于此，设计合成新型、高性能，能在同一个电解质中实现高效析氢和析氧的非贵金属材料的双功能电催化剂，成为当今材料科学与新能源领域的研究热点。Full electrolysis of water in the same electrolyte to produce hydrogen and oxygen is an effective solution to energy shortage and environmental pollution, but it also faces huge challenges. In this field, designing and obtaining high-performance bifunctional electrocatalytic electrode materials for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) has been the goal of researchers. At present, noble metal (Pt, IrO 2 and RuO 2 , etc.) catalysts have high surface activity and excellent catalytic performance for HER and OER, but their high cost and limited reserves cannot meet the actual needs. Therefore, in recent years, the development of carbides, chlorides, sulfides, and phosphides composed of transition metal elements as efficient and environmentally friendly HER catalysts, and oxides and phosphates composed of transition metal elements as high-efficiency OER electrocatalysts have become current research. hotspot. However, when these catalysts are used as both OER and HER bifunctional catalysts in the same electrolyte, there are problems such as low activity and poor stability, which limit their large-scale application. Based on this, the design and synthesis of new, high-performance bifunctional electrocatalysts that can realize efficient hydrogen evolution and oxygen evolution in the same electrolyte have become a research hotspot in the field of materials science and new energy.

发明内容Contents of the invention

本发明的目的，是为了解决现有析氧和析氢反应催化剂在同一电解质中用作双功能催化剂时，存在的催化电流密度低，过电位较高，稳定性差等问题，提供一种过渡金属掺杂的具有超薄纳米片复合纳米线多级结构阵列的全分解水电催化剂，极大地降低了析氧反应和析氢反应的过电势和起峰电位，为全分解水体系催化剂的功能导向性设计与性能优化提供了新的思路和策略。The object of the present invention is to provide a transition metal doped catalyst to solve the problems of low catalytic current density, high overpotential and poor stability when the existing oxygen evolution and hydrogen evolution reaction catalysts are used as dual-functional catalysts in the same electrolyte. The heterogeneous total water splitting electrocatalyst with ultra-thin nanosheet composite nanowire multi-level structure array greatly reduces the overpotential and peak potential of the oxygen evolution reaction and hydrogen evolution reaction, which is the function-oriented design and development of catalysts for the total water splitting system Performance optimization provides new ideas and strategies.

本发明通过如下技术方案予以实现。The present invention is realized through the following technical solutions.

一种酸性全分解水电催化剂的制备方法，具体步骤如下：A kind of preparation method of acidic total decomposition water electrocatalyst, concrete steps are as follows:

(1)将导电基底在1摩尔/升～5摩尔/升的盐酸中超声清洗5～20分钟，然后转移至丙酮溶液中超声清洗5～20分钟，再转移至乙醇溶液中超声清洗5～20分钟，最后用去离子水冲洗导电基底表面，再放到25～80℃的烘箱中干燥60～180分钟。(1) Ultrasonic clean the conductive substrate in 1 mol/L-5 mol/L hydrochloric acid for 5-20 minutes, then transfer to an acetone solution for ultrasonic cleaning for 5-20 minutes, then transfer to an ethanol solution for ultrasonic cleaning for 5-20 minutes Minutes, and finally rinse the surface of the conductive substrate with deionized water, and then put it in an oven at 25-80°C to dry for 60-180 minutes.

(2)配制具有可溶性钴盐、可溶性锰盐、氟化铵和尿素的第一水溶液，所述可溶性钴盐浓度为0.001-0.01摩尔/升，可溶性锰盐浓度为0.0005-0.01摩尔/升，氟化铵浓度为0.01-0.1摩尔/升，尿素浓度为0.0125-0.1摩尔/升，所述可溶性钴盐和锰盐为硝酸盐、硫酸盐或醋酸盐中的任何一种；(2) preparation has the first aqueous solution of soluble cobalt salt, soluble manganese salt, ammonium fluoride and urea, and described soluble cobalt salt concentration is 0.001-0.01 mole/liter, and soluble manganese salt concentration is 0.0005-0.01 mole/liter, fluorine The ammonium chloride concentration is 0.01-0.1 mol/liter, the urea concentration is 0.0125-0.1 mol/liter, and the soluble cobalt salt and manganese salt are any one of nitrate, sulfate or acetate;

将上述第一溶液磁力搅拌5～30分钟后转移至反应釜中，再将步骤(1)处理后的导电基底倾斜放入第一反应釜中，然后密闭该反应釜，升温至80℃～200℃，在自生压力下进行第一次水热反应，反应时间为5～20小时，以在该导电基底表面上垂直生长锰钴碱式碳酸盐纳米线阵列；Stir the above first solution magnetically for 5-30 minutes and then transfer it to the reaction kettle, then put the conductive substrate treated in step (1) into the first reaction kettle obliquely, then seal the reaction kettle and raise the temperature to 80°C-200°C ℃, carry out the first hydrothermal reaction under autogenous pressure, and the reaction time is 5 to 20 hours, so as to vertically grow manganese-cobalt basic carbonate nanowire arrays on the surface of the conductive substrate;

(3)取出步骤(2)的导电基底，用去离子水冲洗导电基底表面，随后放入25～80℃的烘箱中干燥60～180分钟；(3) Take out the conductive substrate in step (2), rinse the surface of the conductive substrate with deionized water, and then put it into an oven at 25-80°C to dry for 60-180 minutes;

(4)配置具有可溶性钴盐、可溶性锰盐、还原剂、氟化铵和尿素的第二水溶液，所述可溶性钴盐浓度为0.001-0.01摩尔/升，可溶性锰盐浓度为0.0005-0.01摩尔/升，锰离子和钴离子的总离子浓度维持在0.0015摩尔/升，还原剂浓度为0.0005-0.01摩尔/升，氟化铵浓度为0.01-0.1摩尔/升，尿素浓度为0.0125-0.1摩尔/升，所述可溶性钴盐和锰盐为硝酸盐、硫酸盐或醋酸盐中的任何一种，还原剂为柠檬酸钠或抗坏血酸；(4) configure the second aqueous solution with soluble cobalt salt, soluble manganese salt, reducing agent, ammonium fluoride and urea, the concentration of the soluble cobalt salt is 0.001-0.01 mole/liter, and the concentration of the soluble manganese salt is 0.0005-0.01 mole/liter liter, the total ion concentration of manganese ion and cobalt ion is maintained at 0.0015 mol/liter, the concentration of reducing agent is 0.0005-0.01 mol/liter, the concentration of ammonium fluoride is 0.01-0.1 mol/liter, and the concentration of urea is 0.0125-0.1 mol/liter , the soluble cobalt salt and manganese salt are any one of nitrate, sulfate or acetate, and the reducing agent is sodium citrate or ascorbic acid;

将上述第二溶液磁力搅拌5～30分钟后转移至第二反应釜中，再将步骤(3)处理后的导电基底斜置放入第二反应釜中，密封该反应釜，升温至80℃～200℃，在自生压力下进行第二次水热反应，反应时间为5～20小时，以在每个所述锰钴碱式碳酸盐纳米线表面上进行二次生长锰钴碱式碳酸盐纳米片，形成锰钴碱式碳酸盐纳米片复合纳米线多级结构；Stir the above second solution magnetically for 5-30 minutes and then transfer it to the second reaction kettle, then place the conductive substrate treated in step (3) obliquely into the second reaction kettle, seal the reaction kettle, and raise the temperature to 80°C ～200°C, carry out the second hydrothermal reaction under autogenous pressure, and the reaction time is 5～20 hours, so as to perform secondary growth of manganese-cobalt basic carbonate nanowires on the surface of each manganese-cobalt basic carbon Carbonate nanosheets, forming a multi-level structure of manganese-cobalt basic carbonate nanosheets composite nanowires;

(5)再次取出步骤(4)该导电基底，用去离子水冲洗该导电基底表面，然后放到25～80℃的烘箱中干燥60～180分钟；(5) Take out the conductive substrate in step (4) again, rinse the surface of the conductive substrate with deionized water, and then dry it in an oven at 25-80°C for 60-180 minutes;

(6)在管式炉的石英管中放置两个瓷舟，将步骤(5)处理后的导电基底放到石英管下方的瓷舟中，同时在石英管上端靠近进气口的瓷舟中放入磷源，于氮气或者氩气气氛中、在200～1000℃煅烧0.5～8小时，然后冷却至室温，使得锰钴碱式碳酸盐超薄纳米片复合纳米线多级结构转变为掺锰的磷化钴超薄纳米片复合纳米线多级结构的酸性全分解水电催化剂，命名为1D/2D Mn-CoP。(6) Place two porcelain boats in the quartz tube of the tube furnace, put the conductive substrate processed in step (5) into the porcelain boat below the quartz tube, and place the porcelain boat near the air inlet at the upper end of the quartz tube Putting in a phosphorus source, calcining at 200-1000°C for 0.5-8 hours in a nitrogen or argon atmosphere, and then cooling to room temperature, so that the multi-level structure of manganese-cobalt basic carbonate ultra-thin nanosheet composite nanowires is transformed into doped Manganese cobalt phosphide ultrathin nanosheet composite nanowire hierarchical structure acidic total hydrolysis electrocatalyst, named 1D/2D Mn-CoP.

所述步骤(1)的导电基底为泡沫镍既NF、钛片或碳布中的任何一种。The conductive substrate in the step (1) is any one of nickel foam, NF, titanium sheet or carbon cloth.

所述步骤(6)的磷源为次磷酸钠、磷酸钠。The phosphorus source of described step (6) is sodium hypophosphite, sodium phosphate.

本发明的有益效果如下：The beneficial effects of the present invention are as follows:

该制备方法由简单的水热反应和低温磷化处理组成，步骤简单、反应时间短、操作方便，对环境非常友好、可重复性强；本发明的材料是酸性全分解水中极好的双功能电催化剂，当电流密度为10mA/cm2时，过电势为0.35V，同时也是酸性析氢反应中极好的电催化剂，当电流密度为10mA/cm2时，过电势是0.042V，接近于商业Pt/C催化剂，且稳定性极好。本发明的材料由于掺杂效应，通过引入外来过渡金属元素，不仅有利于OH-的吸附，使得氢气易解吸附，降低析氢反应的反应势垒，在固液两相之间形成超疏气界面，另外由于超薄纳米片复合纳米线多级结构的存在大大增加电极活性材料的比表面积，提供了更多的活性位点，这些因素协同增强了该材料在酸性全分解水反应中的电催化能力。The preparation method is composed of simple hydrothermal reaction and low-temperature phosphating treatment, the steps are simple, the reaction time is short, the operation is convenient, the environment is very friendly, and the repeatability is strong; the material of the present invention is an excellent dual-function in acidic water decomposition Electrocatalyst, when the current density is 10mA/ cm2 , the overpotential is 0.35V, and it is also an excellent electrocatalyst in the acidic hydrogen evolution reaction. When the current density is 10mA/ cm2 , the overpotential is 0.042V, which is close to commercial Pt/C catalyst with excellent stability. Due to the doping effect, the material of the present invention not only facilitates the adsorption of OH- by introducing foreign transition metal elements, but also makes hydrogen easy to desorb, reduces the reaction barrier of the hydrogen evolution reaction, and forms a super-gas-repellent interface between the solid-liquid two phases , in addition, due to the existence of the multi-level structure of ultrathin nanosheets composite nanowires, the specific surface area of the electrode active material is greatly increased, providing more active sites, and these factors synergistically enhance the electrocatalysis of the material in the acidic total water splitting reaction. ability.

附图说明Description of drawings

图1是实施例1的过渡金属掺杂的具有超薄纳米片复合纳米线多级结构阵列的全分解水电催化剂的结构示意图；Fig. 1 is the structural schematic diagram of the transition metal-doped full-scale water electrocatalyst with ultra-thin nanosheet composite nanowire multi-level structure array of embodiment 1;

图2是对比实施例的一次水热生长磷化处理后的锰掺杂的磷化钴材料(命名为1DMn-CoP)的扫描电镜图(SEM)；Fig. 2 is the scanning electron micrograph (SEM) of the manganese-doped cobalt phosphide material (named 1DMn-CoP) after a hydrothermal growth phosphating treatment of the comparative example;

图3是实施例1中所示的材料的扫描电镜照片图(SEM)；Fig. 3 is the scanning electron micrograph figure (SEM) of the material shown in embodiment 1;

图4是实施例1中所示的材料的高倍的扫描电镜图(SEM)；Fig. 4 is the scanning electron micrograph (SEM) of the high magnification of the material shown in embodiment 1;

图5是实施例1中所示的材料的低倍投射电镜图(TEM)；Figure 5 is a low magnification transmission electron microscope image (TEM) of the material shown in Example 1;

图6是实施例1中所示的材料的高分辨投射电镜图(HRTEM)；Figure 6 is a high resolution transmission electron microscope image (HRTEM) of the material shown in Example 1;

图7a是实施例2的生长在碳布上的锰掺杂的磷化钴多级结构的低倍扫描电镜图(SEM)；图7b是实施例2的生长在碳布上的锰掺杂的磷化钴多级结构的高倍扫描电镜图(SEM)；Fig. 7 a is the low-magnification scanning electron micrograph (SEM) of the manganese-doped cobalt phosphide multilevel structure grown on the carbon cloth of embodiment 2; Fig. 7 b is the manganese-doped cobalt phosphide grown on the carbon cloth of embodiment 2 High-magnification scanning electron microscope (SEM) image of cobalt phosphide hierarchical structure;

图8是实施例2中所示的材料在酸性条件下析氢反应的极化曲线(LSV)图，参比电极为可逆氢电极；Fig. 8 is the polarization curve (LSV) figure of the hydrogen evolution reaction of the material shown in Example 2 under acidic conditions, and the reference electrode is a reversible hydrogen electrode;

图9是实施例1中所示的材料的X射线衍射图(XRD)；Figure 9 is an X-ray diffraction pattern (XRD) of the material shown in Example 1;

图10是实施例1中所示的材料的钴元素的X射线光电子能谱图(XPS)；Fig. 10 is the X-ray photoelectron energy spectrogram (XPS) of the cobalt element of the material shown in embodiment 1;

图11是实施例1中所示的材料的锰元素的X射线光电子能谱图(XPS)；Fig. 11 is the X-ray photoelectron energy spectrogram (XPS) of the manganese element of the material shown in embodiment 1;

图12是实施例1中所示的材料的磷元素的X射线光电子能谱图(XPS)；Fig. 12 is the X-ray photoelectron spectrum (XPS) of the phosphorus element of the material shown in embodiment 1;

图13是实施例1中所示的材料的X射线微区能谱图(EDS)；Fig. 13 is the X-ray microregion energy spectrum (EDS) of the material shown in embodiment 1;

图14是泡沫镍基底、对比实施例中所示的材料、实施例1中所示的材料和Pt/C在酸性条件下析氢反应的极化曲线(LSV)对比图，参比电极为可逆氢电极；Figure 14 is a comparison diagram of the polarization curve (LSV) of the nickel foam substrate, the material shown in the comparative example, the material shown in Example 1, and Pt/C under acidic conditions for the hydrogen evolution reaction, and the reference electrode is reversible hydrogen electrode;

图15是泡沫镍基底、对比实施例中所示的材料、实施例1中所示的材料和Pt/C在酸性条件下的塔菲尔曲线斜率(Tafel)比较图；Fig. 15 is a comparison diagram of the Tafel curve slope (Tafel) under acidic conditions for a nickel foam substrate, materials shown in comparative examples, materials shown in Example 1, and Pt/C;

图16是泡沫镍基底、对比实施例中所示的材料、实施例1中所示的材料和Pt/C在酸性条件下的电化学比表面对比图；Fig. 16 is the electrochemical specific surface contrast figure of nickel foam substrate, the material shown in the comparative example, the material shown in embodiment 1 and Pt/C under acidic conditions;

图17是对比实施例中所示的材料、实施例1中所示的材料和IrO2在酸性条件下析氧反应的极化曲线(LSV)对比图，参比电极为可逆氢电极；Fig. 17 is the material shown in the comparative example, the material shown in the embodiment 1 and IrO Under acidic conditions, the polarization curve (LSV) comparison figure of the oxygen evolution reaction, the reference electrode is a reversible hydrogen electrode;

图18是对比实施例中所示的材料、实施例1中对应的材料和IrO2在酸性条件下析氧反应的塔菲尔曲线斜率(Tafel)比较图；Fig. 18 is the comparison figure of the Tafel curve slope (Tafel) of the material shown in the comparative example, the corresponding material and IrO in the embodiment 1 oxygen evolution reaction under acidic conditions;

图19是Pt/C作为阴极IrO2作为阳极和实施例1中所示的材料同时作为阳极和阴极的酸性全分解水反应的极化曲线(LSV)对比图；Fig. 19 is Pt/C as negative electrode IrO As the anode and the material shown in embodiment 1 simultaneously as the polarization curve (LSV) comparison diagram of the acidic total water splitting reaction of anode and cathode;

图20是实施例1中所示的材料作为阳极和阴极进行全分解水的恒压稳定性测试图；Fig. 20 is a constant pressure stability test diagram of the material shown in Example 1 as the anode and the cathode for fully splitting water;

图21是实施例3中所示的材料在酸性条件下析氢反应的极化曲线(LSV)图。Figure 21 is a polarization curve (LSV) plot of the hydrogen evolution reaction of the material shown in Example 3 under acidic conditions.

具体实施方式detailed description

下面通过具体实施例对本发明作进一步描述，实施例仅仅是示例性的，而非限制性的。The present invention will be further described below through specific examples, and the examples are only illustrative, not restrictive.

实施例1Example 1

导电基底为泡沫镍，磷源为次磷酸钠，还原剂是柠檬酸钠。The conductive substrate is nickel foam, the phosphorus source is sodium hypophosphite, and the reducing agent is sodium citrate.

(1)清洗泡沫镍导电基底，以去除表面上的污垢和杂质。先在3摩尔/升的盐酸中超声清洗10分钟，然后转移至丙酮溶液中超声清洗10分钟，再转移至乙醇溶液中超声清洗10分钟，最后用去离子水多次冲洗导电基底表面，再放到60℃的烘箱中干燥60分钟；(1) Clean the nickel foam conductive substrate to remove dirt and impurities on the surface. First, ultrasonically clean in 3 mol/L hydrochloric acid for 10 minutes, then transfer to acetone solution for ultrasonic cleaning for 10 minutes, then transfer to ethanol solution for ultrasonic cleaning for 10 minutes, and finally rinse the surface of the conductive substrate with deionized water several times, and then put Dry in an oven at 60°C for 60 minutes;

(2)配制包含0.001摩尔/升的硝酸钴、0.0005摩尔/升的硝酸锰、0.0125摩尔/升的氟化铵和0.01摩尔/升的尿素的第一水溶液，磁力搅拌15分钟后转移至反应釜中，再将经过步骤(1)处理的泡沫镍倾斜放入反应釜中，然后密闭该反应釜，升温至100℃，在自生压力下进行第一次水热反应，反应时间为12小时，以在该泡沫镍表面上垂直该基底生长锰钴碱式碳酸盐纳米线阵列；(2) Prepare the first aqueous solution comprising 0.001 mol/liter of cobalt nitrate, 0.0005 mol/liter of manganese nitrate, 0.0125 mol/liter of ammonium fluoride and 0.01 mol/liter of urea, and transfer to the reactor after magnetic stirring for 15 minutes In the process, the foamed nickel processed through step (1) is put into the reaction kettle obliquely, then the reaction kettle is closed, the temperature is raised to 100° C., and the first hydrothermal reaction is carried out under autogenous pressure. The reaction time is 12 hours, with growing a manganese-cobalt basic carbonate nanowire array perpendicular to the substrate on the nickel foam surface;

(3)取出该泡沫镍导电基底，用去离子水冲洗泡沫镍导电基底表面，随后放入60℃的烘箱中干燥60分钟；(3) Take out the nickel foam conductive substrate, rinse the surface of the nickel foam conductive substrate with deionized water, and then put it into an oven at 60° C. to dry for 60 minutes;

(4)配置包含包含0.001摩尔/升的硝酸钴、0.0005摩尔/升的柠檬酸钠、0.0005摩尔/升的硝酸锰、0.0125摩尔/升的氟化铵和0.01摩尔/升的尿素第二水溶液，磁力搅拌15分钟后转移至第二反应釜中，再将步骤(3)处理后的泡沫镍导电基底斜置放入第二反应釜中，密封该反应釜，升温至100℃，在自生压力下进行第二次水热反应，反应时间为10小时，以在每个所述锰钴碱式碳酸盐纳米线表面上进行二次生长锰钴碱式碳酸盐纳米片，形成锰钴碱式碳酸盐纳米片复合纳米线多级结构；(4) configuration comprises the second aqueous solution of urea comprising 0.001 mol/liter of cobalt nitrate, 0.0005 mol/liter of sodium citrate, 0.0005 mol/liter of manganese nitrate, 0.0125 mol/liter of ammonium fluoride and 0.01 mol/liter of urea, After magnetic stirring for 15 minutes, transfer to the second reaction kettle, then place the foamed nickel conductive substrate treated in step (3) obliquely into the second reaction kettle, seal the reaction kettle, raise the temperature to 100°C, and under autogenous pressure Carry out the hydrothermal reaction for the second time, and the reaction time is 10 hours, to carry out secondary growth manganese-cobalt basic carbonate nanosheet on the surface of each described manganese-cobalt basic carbonate nanowire, form manganese-cobalt basic carbonate nanosheet Carbonate nanosheet composite nanowire hierarchical structure;

(5)再次取出该泡沫镍导电基底，用去离子水多次冲洗改导电基底表面，然后放到60℃的烘箱中干燥60分钟；(5) Take out the foamed nickel conductive substrate again, rinse the surface of the modified conductive substrate with deionized water several times, and then dry it in an oven at 60° C. for 60 minutes;

(6)在管式炉的石英管中放置两个瓷舟，将步骤(5)处理后的导电基底放到石英管中下方的瓷舟中，同时在石英管上端靠近进气口的瓷舟中放入次磷酸钠，于氩气气氛中、在300℃的管式炉中煅烧3小时，然后冷却至室温，使得锰钴碱式碳酸盐超薄纳米片复合纳米线多级结构转变为掺锰的磷化钴超薄纳米片复合纳米线多级结构的酸性全分解水电催化剂，命名为1D/2D Mn-CoP。(6) Place two porcelain boats in the quartz tube of the tube furnace, put the conductive substrate processed in step (5) into the porcelain boat at the bottom of the quartz tube, and place the porcelain boat near the air inlet at the upper end of the quartz tube Put sodium hypophosphite in it, calcinate in a tube furnace at 300°C in an argon atmosphere for 3 hours, and then cool to room temperature, so that the multi-level structure of manganese-cobalt basic carbonate ultra-thin nanosheet composite nanowires is transformed into Manganese-doped cobalt phosphide ultrathin nanosheet composite nanowire hierarchical structure acidic total water splitting electrocatalyst, named 1D/2D Mn-CoP.

采用三电极体系测试该材料在0.5摩尔/升的硫酸溶液中的析氧、析氢和全分解水性能，其中，对电极是铂片，参比电极是可逆氢电极，扫描速率是5mV/s。A three-electrode system was used to test the oxygen evolution, hydrogen evolution and total water splitting performance of the material in a 0.5 mol/L sulfuric acid solution, wherein the counter electrode was a platinum sheet, the reference electrode was a reversible hydrogen electrode, and the scan rate was 5mV/s.

图1是实施例1的1D/2D Mn-CoP的结构示意图，可以看出纳米片均匀生长在纳米线表面，这样的多级结构以阵列的形式垂直生长在导电基底表面。Figure 1 is a schematic diagram of the structure of 1D/2D Mn-CoP in Example 1. It can be seen that nanosheets grow uniformly on the surface of nanowires, and such a multi-level structure grows vertically on the surface of a conductive substrate in the form of an array.

图3是实施例1的1D/2D Mn-CoP的低倍扫描电镜图(SEM)，其中清楚地显示出，超薄纳米片复合纳米线多级结构阵列垂直于泡沫镍表面均匀生长。Fig. 3 is a low magnification scanning electron microscope image (SEM) of 1D/2D Mn-CoP of Example 1, which clearly shows that the ultrathin nanosheet composite nanowire hierarchical structure array grows uniformly perpendicular to the nickel foam surface.

图4是实施例1的1D/2D Mn-CoP的高倍扫描电镜图(SEM)，可以看出纳米线表面均匀生长着纳米片，纳米片之间相互交错，形成网络结构；纳米线直径在100-150nm，长度为10-20μm。Fig. 4 is the high magnification scanning electron microscope picture (SEM) of the 1D/2D Mn-CoP of embodiment 1, it can be seen that nanosheets are evenly grown on the surface of the nanowires, and the nanosheets are interlaced to form a network structure; the diameter of the nanowires is 100 -150nm with a length of 10-20μm.

图5是实施例1的1D/2D Mn-CoP的低倍透射电镜图(TEM)，可知与扫描电镜图观测结果一致，经过低温磷化处理后多级结构依然保持。Fig. 5 is a low magnification transmission electron microscope image (TEM) of 1D/2D Mn-CoP of Example 1. It can be seen that the multi-level structure is still maintained after low-temperature phosphating treatment, which is consistent with the observation results of the scanning electron microscope image.

图6是实施例1的1D/2D Mn-CoP的高分辨投射电镜图(HRTEM)，通过测量晶格间距，证明合成的材料为磷化钴，锰的掺杂没有改变磷化钴的晶体结构。Figure 6 is a high-resolution transmission electron microscope image (HRTEM) of the 1D/2D Mn-CoP of Example 1. By measuring the lattice spacing, it is proved that the synthesized material is cobalt phosphide, and the doping of manganese does not change the crystal structure of cobalt phosphide .

图9是实施例1的1D/2D Mn-CoP的X射线衍射图(XRD)，与标准谱图对比可辨别出本发明的材料成分为磷化钴，与高分辨投射电镜图对应。Figure 9 is the X-ray diffraction pattern (XRD) of 1D/2D Mn-CoP of Example 1. Compared with the standard spectrum, it can be identified that the material composition of the present invention is cobalt phosphide, corresponding to the high-resolution transmission electron microscope.

图10是实施例1的1D/2D Mn-CoP的钴元素的X射线光电子能谱图(XPS)，可知钴的价态有+3和+2。10 is an X-ray photoelectron spectrum (XPS) of the cobalt element in the 1D/2D Mn-CoP of Example 1. It can be seen that the valence states of cobalt are +3 and +2.

图11是实施例1的1D/2D Mn-CoP的锰元素的X射线光电子能谱图(XPS)，证明材料中含有锰元素，锰的价态有+3和+2。Fig. 11 is the X-ray photoelectron spectrum (XPS) of the manganese element of 1D/2D Mn-CoP in Example 1, which proves that the material contains manganese element, and the valence states of manganese are +3 and +2.

图12是实施例1的1D/2D Mn-CoP的磷元素的X射线光电子能谱图(XPS)，Co 2p3/2和P 2p3/2对应的位置是典型的磷化钴中的P-Co键。Fig. 12 is the X-ray photoelectron spectrum (XPS) of the phosphorus element of 1D/2D Mn-CoP of embodiment 1, and the position corresponding to Co 2p 3/2 and P 2p 3/2 is the P in typical cobalt phosphide -Co key.

图13是实施例1的1D/2D Mn-CoP的X射线微区能谱图(EDS)，证明材料中含有锰、钴、磷三种元素，锰的掺杂量为1.49％，钴和磷的含量比约为1比1。Figure 13 is the X-ray energy spectrum (EDS) of the 1D/2D Mn-CoP of Example 1, which proves that the material contains three elements: manganese, cobalt and phosphorus, the doping amount of manganese is 1.49%, cobalt and phosphorus The content ratio is about 1:1.

图14是实施例1的1D/2D Mn-CoP、对比实施例的1D Mn-CoP、NF与商业Pt/C的析氢极化曲线对比图，可知1D/2D Mn-CoP在-10mA/cm2对应的过电位是42mV，接近商业Pt/C催化剂。Figure 14 is a comparison of the hydrogen evolution polarization curves of 1D/2D Mn-CoP of Example 1, 1D Mn-CoP of Comparative Example, NF and commercial Pt/C. It can be seen that 1D/2D Mn-CoP is at -10mA/cm 2 The corresponding overpotential is 42 mV, which is close to the commercial Pt/C catalyst.

图15是实施例1的1D/2D Mn-CoP、对比实施例的1D Mn-CoP、NF与商业Pt/C的析氢反应的塔菲尔斜率对比图，可知1D/2D Mn-CoP具有更小的塔菲尔斜率，进而说明1D/2D Mn-CoP具有更快的电化学反应速率。Fig. 15 is a comparison chart of the Tafel slopes of the hydrogen evolution reaction of 1D/2D Mn-CoP of Example 1, 1D Mn-CoP of Comparative Example, NF and commercial Pt/C. It can be seen that 1D/2D Mn-CoP has a smaller The Tafel slope of 1D/2D Mn-CoP has a faster electrochemical reaction rate.

图16是实施例1的1D/2D Mn-CoP、对比实施例的1D Mn-CoP、NF与商业Pt/C在析氢反应时的电化学表面积比较图，可知1D/2D Mn-CoP的电化学比较面最高，电催化活性也最高。Fig. 16 is a comparison diagram of electrochemical surface area of 1D/2D Mn-CoP of Example 1, 1D Mn-CoP of Comparative Example, NF and commercial Pt/C during hydrogen evolution reaction. It can be seen that the electrochemical surface area of 1D/2D Mn-CoP is The comparison surface is the highest, and the electrocatalytic activity is also the highest.

图17是实施例1的1D/2D Mn-CoP、对比实施例的1D Mn-CoP与商业IrO2的析氧反应时的极化曲线对比图，可知1D/2D Mn-CoP在酸性条件下的析氧性能优于1D Mn-CoP和商业IrO2。Figure 17 is a comparison of the polarization curves of the 1D/2D Mn-CoP of Example 1 , the 1D Mn-CoP of Comparative Example and commercial IrO during the oxygen evolution reaction. It can be seen that the 1D/2D Mn-CoP is under acidic conditions. The oxygen evolution performance is better than 1D Mn-CoP and commercial IrO 2 .

图18是实施例1的1D/2D Mn-CoP、对比实施例的1D Mn-CoP、NF与商业Pt/C的析氧反应的塔菲尔斜率对比图，可知1D/2D Mn-CoP具有更小的塔菲尔斜率，进而说明1D/2D Mn-CoP具有更快的电化学反应速率。Figure 18 is a comparison of the Tafel slopes of the oxygen evolution reaction of 1D/2D Mn-CoP of Example 1, 1D Mn-CoP of Comparative Example, NF and commercial Pt/C. It can be seen that 1D/2D Mn-CoP has more The small Tafel slope further indicates that 1D/2D Mn-CoP has a faster electrochemical reaction rate.

图19是Pt/C作为阴极IrO2作为阳极和实施例1的1D/2D Mn-CoP同时作为阳极和阴极的酸性全分解水反应的极化曲线(LSV)对比图。可知1D/2D Mn-CoP同时作为阳极和阴极进行全分解水，当电流达到10mA/cm2时过电位为0.35V。Figure 19 is a comparison diagram of the polarization curve (LSV) of the acidic total water splitting reaction with Pt/C as the cathode, IrO 2 as the anode and the 1D/2D Mn-CoP of Example 1 as both the anode and the cathode. It can be seen that 1D/2D Mn-CoP acts as both anode and cathode to completely split water, and the overpotential is 0.35V when the current reaches 10mA/cm 2 .

图20是实施例1的1D/2D Mn-CoP作为阳极和阴极进行全分解水的恒压稳定性测试图。可知在1.4V的电压下，经过20000秒的恒压测试，该材料产生的电流维持不变。Fig. 20 is a constant pressure stability test diagram of the 1D/2D Mn-CoP of Example 1 as the anode and cathode for total water splitting. It can be seen that under the voltage of 1.4V, after 20000 seconds of constant voltage test, the current generated by the material remains unchanged.

实施例2Example 2

一种过渡金属掺杂的具有超薄纳米片复合纳米线多级结构阵列的酸性全分解水电催化剂的方法，所述导电基底是碳布。A transition metal-doped acidic water-splitting electrocatalyst with ultra-thin nanosheet composite nanowire multi-level structure array, the conductive substrate is carbon cloth.

该电催化材料的制备方法与实施例1基本相同，不同之处在于：将步骤(1)中的导电基底改为碳布。该电催化材料命名为1D/2D Mn-CoP/CC。The preparation method of the electrocatalytic material is basically the same as that of Example 1, except that the conductive substrate in step (1) is changed to carbon cloth. The electrocatalytic material is named 1D/2D Mn-CoP/CC.

图7a是实施例2的1D/2D Mn-CoP/CC的低倍扫描电镜图，可以看到该材料均匀的生长在碳纳米纤维的表面，图7b中可以看出纳米片均匀地生长在纳米线表面，形成纳米片复合纳米线多级结构。Figure 7a is a low-magnification scanning electron microscope image of the 1D/2D Mn-CoP/CC of Example 2. It can be seen that the material grows uniformly on the surface of carbon nanofibers. It can be seen in Figure 7b that the nanosheets grow uniformly on the nanometer On the surface of the wire, a nanosheet composite nanowire hierarchical structure is formed.

图8是实施例2的1D/2D Mn-CoP/CC在酸性条件下析氢反应的极化曲线(LSV)图，从图中可以看出当电流达到-10mA/cm2时，析氢反应相对可逆氢电极的过电位是52mV，表明了该材料极好的催化析氢反应性能。Figure 8 is a polarization curve (LSV) diagram of the hydrogen evolution reaction of 1D/2D Mn-CoP/CC in Example 2 under acidic conditions. It can be seen from the figure that when the current reaches -10mA/cm 2 , the hydrogen evolution reaction is relatively reversible The overpotential of the hydrogen electrode is 52mV, indicating the excellent performance of the material in catalyzing the hydrogen evolution reaction.

实施例3Example 3

该电催化材料的制备方法与实施例1基本相同，不同之处在于：将步骤(1)中的导电基底改为钛片。该材料命名为1D/2D Mn-CoP/Ti。The preparation method of the electrocatalytic material is basically the same as that of Example 1, except that the conductive substrate in step (1) is changed to a titanium sheet. The material is named 1D/2D Mn-CoP/Ti.

图21是1D/2D Mn-CoP/Ti在酸性环境下析氢反应的极化曲线图，从图中可以看出当电流达到-10mA/cm2时，析氢反应相对可逆氢电极的过电位是63mV，表明了该材料极好的催化析氢反应性能。Figure 21 is the polarization curve of the hydrogen evolution reaction of 1D/2D Mn-CoP/Ti in an acidic environment. It can be seen from the figure that when the current reaches -10mA/ cm2 , the overpotential of the hydrogen evolution reaction relative to the reversible hydrogen electrode is 63mV , indicating the excellent performance of the material in catalyzing the hydrogen evolution reaction.

实施例4Example 4

该电催化材料的制备方法与实施例1基本相同，不同之处在于：将步骤(2)和步骤(4)中的硝酸钴的浓度改为0.01摩尔/升。The preparation method of the electrocatalytic material is basically the same as that of Example 1, except that the concentration of cobalt nitrate in step (2) and step (4) is changed to 0.01 mol/liter.

实施例5Example 5

该电催化材料的制备方法与实施例1基本相同，不同之处在于：将步骤(2)和步骤(4)中的硝酸锰的浓度改为0.01摩尔/升。The preparation method of the electrocatalytic material is basically the same as that of Example 1, except that the concentration of manganese nitrate in step (2) and step (4) is changed to 0.01 mol/liter.

实施例6Example 6

该电催化材料的制备方法与实施例1基本相同，不同之处在于：将步骤(6)中氩气气氛改为氮气气氛，煅烧时间由3小时改为0.5小时。The preparation method of the electrocatalytic material is basically the same as that of Example 1, except that the argon atmosphere in step (6) is changed to a nitrogen atmosphere, and the calcination time is changed from 3 hours to 0.5 hours.

对比实施例comparative example

该电催化材料的制备方法与实施例1基本相同，不同之处在于：经过步骤(3)一次水热生长之后直接进行磷化处理，该材料命名为1D Mn-CoP。The preparation method of the electrocatalytic material is basically the same as that of Example 1, except that the phosphating treatment is directly performed after the first hydrothermal growth in step (3), and the material is named 1D Mn-CoP.

图2是1D Mn-CoP的扫描电镜图，可以清楚地看到一维的纳米线以阵列的形式均匀地生长在导电基底表面，并且纳米线表面十分光滑。Figure 2 is a scanning electron microscope image of 1D Mn-CoP. It can be clearly seen that the one-dimensional nanowires grow uniformly on the surface of the conductive substrate in the form of an array, and the surface of the nanowires is very smooth.

图14是对比实施例的1D Mn-CoP的析氢极化曲线图，可知1D Mn-CoP在-10mA/cm2对应的过电位是88mV，与1D/2D Mn-CoP相比析氢过电位要差46mV。Figure 14 is the hydrogen evolution polarization curve of 1D Mn-CoP of the comparative example. It can be seen that the overpotential of 1D Mn-CoP at -10mA/ cm2 is 88mV, which is worse than that of 1D/2D Mn-CoP. 46mV.

图15是对比实施例的1D Mn-CoP析氢反应的塔菲尔斜率图，可知1D Mn-CoP塔菲尔斜率位98mV/dec，说明1DMn-CoP电化学反应速率比1D/2D Mn-CoP要慢。Fig. 15 is the Tafel slope diagram of the 1D Mn-CoP hydrogen evolution reaction of the comparative example. It can be seen that the 1D Mn-CoP Tafel slope position is 98mV/dec, indicating that the electrochemical reaction rate of 1DMn-CoP is faster than that of 1D/2D Mn-CoP slow.

图17是对比实施例的1D Mn-CoP的析氧极化曲线图，可知1D Mn-CoP在100mA/cm2对应的电压为1.68V，析氧性能接近贵金属IrO2。Figure 17 is the oxygen evolution polarization curve of 1D Mn-CoP of the comparative example. It can be seen that the voltage corresponding to 100mA/cm 2 of 1D Mn-CoP is 1.68V, and the oxygen evolution performance is close to that of noble metal IrO 2 .

以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (3)

1. a kind of preparation method of acid full decomposition water elctro-catalyst, comprises the following steps that：
(1) conductive substrates are cleaned by ultrasonic 5~20 minutes in the hydrochloric acid of 1 mol/L~5 mol/L, are then transferred to acetone It is cleaned by ultrasonic 5~20 minutes in solution, transfers in ethanol solution and be cleaned by ultrasonic 5~20 minutes, is finally rushed with deionized water Wash conductive substrates surface, then be put into 25~80 DEG C of baking oven and dry 60~180 minutes.
(2) first aqueous solution with soluble cobalt, soluble manganese salt, ammonium fluoride and urea, the soluble cobalt are prepared Concentration is 0.001-0.01 mol/Ls, and soluble manganese salinity is 0.0005-0.01 mol/Ls, and fluorination ammonium concentration is 0.01- 0.1 mol/L, urea concentration is 0.0125-0.1 mol/Ls, the soluble cobalt and manganese salt be nitrate, sulfate or Any one of acetate；
Above-mentioned first solution magnetic agitation is transferred in reactor after 5~30 minutes, then by the conductive base after step (1) treatment Slanted floor is put into the first reactor, then the closed reactor, is warming up to 80 DEG C~200 DEG C, and is carried out at autogenous pressures Hydro-thermal reaction, the reaction time is 5~20 hours, is received with the vertical-growth manganese cobalt subcarbonate on the conductive substrates surface Nanowire arrays；
(3) conductive substrates of step (2) are taken out, with deionized water rinsing conductive substrates surface, 25~80 DEG C of baking is subsequently placed into Dried 60~180 minutes in case；
(4) second aqueous solution of the configuration with soluble cobalt, soluble manganese salt, reducing agent, ammonium fluoride and urea, described solvable Property cobalt salt concentration be 0.001-0.01 mol/Ls, soluble manganese salinity is 0.0005-0.01 mol/Ls, manganese ion and cobalt from The total ion concentration of son maintains 0.0015 mol/L, and reductant concentration is 0.0005-0.01 mol/Ls, and fluorination ammonium concentration is 0.01-0.1 mol/Ls, urea concentration is 0.0125-0.1 mol/Ls, and the soluble cobalt and manganese salt are nitrate, sulfuric acid Any one of salt or acetate, reducing agent are sodium citrate or ascorbic acid；
Above-mentioned second solution magnetic agitation is transferred in the second reactor after 5~30 minutes, then by step (3) treatment after lead Electric substrate is tilting to be put into the second reactor, seals the reactor, is warming up to 80 DEG C~200 DEG C, and is carried out at autogenous pressures Secondary hydro-thermal reaction, the reaction time is 5~20 hours, and two are carried out with each described manganese cobalt subcarbonate nanowire surface Secondary growth manganese cobalt subcarbonate nanometer sheet, forms manganese cobalt subcarbonate nanometer sheet composite nano-line multilevel hierarchy；
(5) step (4) conductive substrates are taken out again, with the deionized water rinsing conductive substrates surface, are then put into 25~80 DEG C baking oven in dry 60~180 minutes；
(6) two porcelain boats are placed in the quartz ampoule of tube furnace, the conductive substrates after step (5) treatment is put into quartz ampoule lower section Porcelain boat in, while be put into phosphorus source in the porcelain boat of air inlet in quartz ampoule upper end, in nitrogen or argon gas atmosphere, 200~1000 DEG C are calcined 0.5~8 hour, are subsequently cooled to room temperature so that manganese cobalt subcarbonate ultrathin nanometer piece composite Nano Line multilevel hierarchy is changed into the full decomposition water electro-catalysis of acidity of the phosphatization cobalt ultrathin nanometer piece composite nano-line multilevel hierarchy for mixing manganese Agent, is named as 1D/2D Mn-CoP.
2. a kind of preparation method of acid full decomposition water elctro-catalyst according to claim 1, it is characterised in that the step Suddenly the conductive substrates of (1) are nickel foam both any one of NF, titanium sheet or carbon cloth.
3. a kind of preparation method of acid full decomposition water elctro-catalyst according to claim 1, it is characterised in that the step Suddenly the phosphorus source of (6) is sodium hypophosphite, sodium phosphate.
CN201611081350.0A 2016-11-30 2016-11-30 Preparation method of electric catalyst for acidic fully-decomposed water Pending CN106694005A (en)

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