CN114525546A

Movatterモバイル変換

Info

Publication number: CN114525546A
Application number: CN202210328339.9A
Authority: CN
Inventors: 张勇; 姚尚智; 吴玉程; 蔡婧怡; 张雪茹; 崔接武; 舒霞; 王岩; 秦永强
Original assignee: Hefei University of Technology
Current assignee: Hefei University of Technology
Priority date: 2022-03-30
Filing date: 2022-03-30
Publication date: 2022-05-24
Anticipated expiration: 2042-03-30
Also published as: CN114525546B

Abstract

Translated fromChinese

本发明公开了一种二元镍钴硒化物纳米片材料的制备方法，具体步骤如下：以六水硝酸镍和六水硝酸钴为镍源和钴源，以合适比例的去离子水和甲醇为溶剂，先采用水热法合成草酸镍钴前驱体纳米片，然后与硒粉混合并在管式炉中于氩气中煅烧，得到镍钴硒化物纳米片材料。本发明制得的二元镍钴硒化物纳米片材料比表面积较大，导电性较高，用作析氧反应的电催化材料时，极大改善了电化学性能。

The invention discloses a method for preparing a binary nickel-cobalt selenide nanosheet material. The specific steps are as follows: using nickel nitrate hexahydrate and cobalt nitrate hexahydrate as nickel source and cobalt source, and using appropriate proportion of deionized water and methanol as Solvent, firstly adopting the hydrothermal method to synthesize nickel-cobalt oxalate precursor nanosheets, then mixing with selenium powder and calcining in argon in a tube furnace to obtain nickel-cobalt selenide nanosheet material. The binary nickel-cobalt selenide nanosheet material prepared by the invention has a larger specific surface area and higher conductivity, and when used as an electrocatalytic material for an oxygen evolution reaction, the electrochemical performance is greatly improved.

Description

Translated fromChinese

一种二元镍钴硒化物纳米片材料的制备方法A kind of preparation method of binary nickel cobalt selenide nanosheet material

技术领域technical field

本发明涉及电化学催化剂材料制备技术领域，具体涉及一种二元镍钴硒化物纳米片材料的制备方法。The invention relates to the technical field of electrochemical catalyst material preparation, in particular to a preparation method of a binary nickel-cobalt selenide nanosheet material.

背景技术Background technique

随着经济的快速发展，人们对于能源的需求日益增加。由于化石能源的不可再生和对环境的污染，所以人们迫切需求新的绿色能源。通过电解水去获得氢气与氧气是一种受到广泛关注的解决方案，但是制约这一方案的关键因素就是析氧反应时缓慢的动力学。目前，市面上最高效的析氧电催化剂的主要成分是贵金属及其氧化物，但是由于高昂的价格和稀缺的储量使其难以大规模应用于工业。目前，过渡金属氧化物由于合成方便、产量大、储量高、价格便宜等优点越来越受到关注，其中镍钴化合物具有二价镍/三价镍和二价钴/三价钴两对氧化还原对，从而更有利于析氧反应的进行。镍钴硒化物材料由于具有较高的本征电导率和载流子传递速率而吸引了越来越多的研究者的青睐。With the rapid economic development, people's demand for energy is increasing. Due to the non-renewable nature of fossil energy and the pollution to the environment, people are in urgent need of new green energy. Obtaining hydrogen and oxygen by electrolysis of water is a solution that has received extensive attention, but the key factor restricting this solution is the slow kinetics of the oxygen evolution reaction. At present, the main components of the most efficient oxygen evolution electrocatalysts on the market are noble metals and their oxides, but the high price and scarce reserves make it difficult for large-scale industrial application. At present, transition metal oxides have attracted more and more attention due to their advantages of convenient synthesis, large output, high reserves, and low price. Among them, nickel-cobalt compounds have two redox pairs of divalent nickel/trivalent nickel and divalent cobalt/trivalent cobalt. Yes, which is more conducive to the oxygen evolution reaction. Nickel-cobalt selenide materials have attracted more and more researchers due to their high intrinsic conductivity and carrier transfer rate.

传统的硒化物制造方法是预先制备出金属氧化物，随后通过湿化学方法将氧化物转变成硒化物，这种方法不仅过程繁琐，产率低，且硒化后会留下大量的废液，污染环境。所以研究者们迫切需要一种简便而高效的制造高导电率和高活性位点数量的镍钴硒化物材料方法。The traditional manufacturing method of selenide is to prepare metal oxide in advance, and then convert the oxide into selenide by wet chemical method. This method is not only cumbersome and low in yield, but also leaves a large amount of waste liquid after selenization. polluted environment. Therefore, researchers urgently need a facile and efficient method to fabricate nickel-cobalt selenide materials with high conductivity and high number of active sites.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于提供一种二元镍钴硒化物纳米片材料的制备方法，该方法使用的原料简单易得，生产成本低廉，产率高，无污染，适合大规模工业化生产，具有很好的商业前景。The purpose of the present invention is to provide a method for preparing a binary nickel-cobalt selenide nanosheet material, which uses simple and easy-to-obtain raw materials, low production cost, high yield, no pollution, is suitable for large-scale industrial production, and has good business prospects.

为实现上述目的，本发明提供如下技术方案：To achieve the above object, the present invention provides the following technical solutions:

一种二元镍钴硒化物纳米片材料的制备方法，由水热反应制备出二元镍钴前驱体溶液，然后采用硒化退火法制备得到所述二元镍钴硒化物纳米片材料，镍钴硒化物纳米片长度为600-700nm，宽度为200-300nm，整体由多层纳米片叠层形成。A method for preparing a binary nickel-cobalt selenide nanosheet material, wherein a binary nickel-cobalt precursor solution is prepared by a hydrothermal reaction, and then the binary nickel-cobalt selenide nanosheet material is prepared by a selenization annealing method; The cobalt selenide nanosheet has a length of 600-700 nm and a width of 200-300 nm, and is formed by stacking multiple layers of nanosheets as a whole.

优选地，所述水热反应具体包括以下步骤：Preferably, the hydrothermal reaction specifically comprises the following steps:

(1)将草酸置于去离子水中进行磁力搅拌，然后将草酸溶液置于超声器中进行超声分散；(1) oxalic acid is placed in deionized water to carry out magnetic stirring, and then oxalic acid solution is placed in a supersonicator to carry out ultrasonic dispersion;

(2)将硝酸镍、硝酸钴加入到甲醇中，超声并搅拌得到硝酸盐溶液；(2) adding nickel nitrate and cobalt nitrate into methanol, ultrasonically and stirring to obtain nitrate solution;

(3)将步骤(2)配制的溶液倒入步骤(1)配制的溶液中，然后将混合溶液搅拌5～10min，得到二元镍钴前驱体溶液。(3) Pour the solution prepared in step (2) into the solution prepared in step (1), and then stir the mixed solution for 5-10 minutes to obtain a binary nickel-cobalt precursor solution.

优选地，所述步骤(1)的具体过程如下，将草酸置于去离子水中进行磁力搅拌5～10min，搅拌速度为600～800r/min，然后将草酸溶液置于超声器中进行超声分散5～10min。Preferably, the specific process of the step (1) is as follows, the oxalic acid is placed in deionized water for magnetic stirring for 5 to 10 min, and the stirring speed is 600 to 800 r/min, and then the oxalic acid solution is placed in an ultrasonic device for ultrasonic dispersion 5 ~10min.

优选地，所述步骤(2)中，超声5～10min，磁力搅拌5～10min，搅拌速度为600～800r/min，得到的硝酸盐溶液中镍钴离子的摩尔比为1:2。Preferably, in the step (2), ultrasonication is performed for 5-10 minutes, magnetic stirring is performed for 5-10 minutes, and the stirring speed is 600-800 r/min, and the molar ratio of nickel-cobalt ions in the obtained nitrate solution is 1:2.

优选地，所述草酸为3mmol，去离子水为20ml，硝酸镍为1mmol，硝酸钴为2mmol，甲醇为40ml。Preferably, the oxalic acid is 3 mmol, the deionized water is 20 ml, the nickel nitrate is 1 mmol, the cobalt nitrate is 2 mmol, and the methanol is 40 ml.

优选地，所述步骤(1)中的去离子水与步骤(2)中的甲醇的体积比为1:2。Preferably, the volume ratio of the deionized water in the step (1) to the methanol in the step (2) is 1:2.

优选地，所述硒化退火法具体包括以下步骤：Preferably, the selenization annealing method specifically includes the following steps:

(1)将二元镍钴前驱体溶液加入到高压反应釜内胆中，将内胆旋好放入高压反应釜外壳中，将高压反应釜放入真空干燥箱，加热到115～125℃，保持20～25h；水热反应结束后，通过离心分离沉淀物，用去离子水和乙醇分别洗涤2～4次，然后置于真空干燥箱中干燥；(1) adding the binary nickel-cobalt precursor solution into the inner liner of the autoclave, screwing the inner liner into the outer shell of the autoclave, putting the autoclave into the vacuum drying oven, heating to 115～125 ℃, Keep for 20 to 25 hours; after the hydrothermal reaction is over, the precipitate is separated by centrifugation, washed with deionized water and ethanol for 2 to 4 times, and then placed in a vacuum drying box to dry;

(2)将步骤(1)中所得产物与硒粉混合，置于管式炉中于氩气气氛下进行退火，自然冷却后得到所述二元镍钴硒化物纳米片材料。(2) The product obtained in step (1) is mixed with selenium powder, placed in a tube furnace for annealing under an argon atmosphere, and naturally cooled to obtain the binary nickel cobalt selenide nanosheet material.

优选地，所述步骤(1)中，水热反应后，干燥条件如下，干燥温度为55～65℃，干燥时间为10～14h。Preferably, in the step (1), after the hydrothermal reaction, the drying conditions are as follows, the drying temperature is 55-65° C., and the drying time is 10-14 h.

优选地，所述步骤(2)中，煅烧温度为300～350℃，升温速率为5～10℃/min，保温时间为0.5～1h。Preferably, in the step (2), the calcination temperature is 300-350° C., the heating rate is 5-10° C./min, and the holding time is 0.5-1 h.

优选地，所述步骤(2)中，保温时间为2h，氩气流量为80～100sccm，随炉冷却，目的是使得硒粉升华，有利于纳米颗粒片的硒化。Preferably, in the step (2), the holding time is 2h, the argon flow rate is 80-100sccm, and the furnace is cooled to sublimate the selenium powder, which is beneficial to the selenization of the nanoparticle sheet.

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

1、本发明的二元镍钴硒化物纳米片材料具有多层纳米片结构，可有效提高电化学活性面积，改善电荷传输速度和物质扩散，加快反应动力学过程，大幅提高材料的电化学性能；1. The binary nickel cobalt selenide nanosheet material of the present invention has a multi-layer nanosheet structure, which can effectively increase the electrochemical active area, improve the charge transfer speed and material diffusion, accelerate the reaction kinetic process, and greatly improve the electrochemical performance of the material. ;

2、本发明的二元镍钴硒化物纳米片材料由NiSe₂与CoSe₂复合而成，NiSe₂/CoSe₂二元异质材料中的双金属中心的氧化还原对可以显著增强材料的电化学活性，NiSe₂与CoSe₂的协同效应可以优化反应动力学；2. The binary nickel cobalt selenide nanosheet material of the present invention is composed of NiSe₂ and CoSe₂ , and the redox pair of the bimetallic center in the NiSe₂ /CoSe₂ binary heterogeneous material can significantly enhance the electrochemical performance of the material. Activity, the synergistic effect of NiSe₂ and CoSe₂ can optimize the reaction kinetics;

3、本发明的二元镍钴硒化物纳米片材料富含高比例的高价金属离子Ni³⁺与Co³⁺,增强了OH^-的化学吸附，促进了电子转移，与单金属催化剂相比，双金属催化剂具有更好的动力学促进作用；3. The binary nickel-cobalt selenide nanosheet material of the present invention is rich in high proportion of high-valent metal ions Ni³⁺ and Co³⁺ , which enhances the chemical adsorption of OH^- and promotes electron transfer. Compared with single-metal catalysts, Bimetallic catalysts have better kinetic promotion;

4、本发明的二元镍钴硒化物纳米片材料具备优秀的电催化析氧性能，在电流密度为10mA/cm^-2时能达到310mV的过电势，具有商业应用前景；4. The binary nickel-cobalt selenide nanosheet material of the present invention has excellent electrocatalytic oxygen evolution performance, and can reach an overpotential of 310mV when the current density is 10mA/cm^-2 , and has commercial application prospects;

5、本发明使用的硒化退火法制备出稳定的多层结构，避免了传统的湿化学硒化法制备硒化物所带来的废液污染与低产率的问题，这种制备方法简单、稳定、产率高、无污染，有利于大规模工业化生产，可应用于电催化析氧材料。5. The selenization annealing method used in the present invention prepares a stable multi-layer structure, which avoids the problems of waste liquid pollution and low yield caused by the traditional wet chemical selenization method for preparing selenide. This preparation method is simple and stable. , high yield, no pollution, conducive to large-scale industrial production, can be used in electrocatalytic oxygen evolution materials.

附图说明Description of drawings

图1是实施例1-3制备得到的二元镍钴硒化物纳米片材料的X射线衍射图(XRD)；Fig. 1 is the X-ray diffraction pattern (XRD) of the binary nickel cobalt selenide nanosheet material prepared by embodiment 1-3;

图2是实施例2制备得到的二元镍钴硒化物纳米片材料低倍下的扫描电镜图(SEM)；Fig. 2 is the scanning electron microscope image (SEM) under low magnification of the binary nickel-cobalt selenide nanosheet material prepared in Example 2;

图3是实施例2制备得到的二元镍钴硒化物纳米片材料的X射线光电子能谱图(XPS)的Co 2p分峰图；Fig. 3 is theCo 2p peak figure of the X-ray photoelectron spectroscopy (XPS) of the binary nickel cobalt selenide nanosheet material prepared in Example 2;

图4是实施例2制备得到的二元镍钴硒化物纳米片材料的X射线光电子能谱图(XPS)的Ni 2p分峰图；Fig. 4 is theNi 2p peak figure of the X-ray photoelectron spectroscopy (XPS) of the binary nickel cobalt selenide nanosheet material prepared in Example 2;

图5是实施例2制备得到的二元镍钴硒化物纳米片材料的X射线光电子能谱图(XPS)的O1s分峰图；Fig. 5 is the O1s peak figure of the X-ray photoelectron spectroscopy (XPS) of the binary nickel cobalt selenide nanosheet material prepared in Example 2;

图6是实施例2制备得到的二元镍钴硒化物纳米片材料的X射线光电子能谱图(XPS)的Se 3d分峰图；Fig. 6 is the Se 3d peak figure of the X-ray photoelectron spectroscopy (XPS) of the binary nickel cobalt selenide nanosheet material prepared in Example 2;

图7是实施例1-3制备得到的二元镍钴硒化物纳米片材料的电解水析氧的线性扫描曲线图(LSV)。7 is a linear scan curve (LSV) of oxygen evolution in electrolyzed water of the binary nickel cobalt selenide nanosheet materials prepared in Examples 1-3.

具体实施方式Detailed ways

下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

实施例1Example 1

一种二元镍钴硒化物纳米片材料的制备方法，包括以下步骤：A preparation method of binary nickel cobalt selenide nanosheet material, comprising the following steps:

(1)将3mmol草酸置于20ml去离子水中进行磁力搅拌5min，搅拌速度为600r/min，然后将草酸溶液置于超声器中进行超声分散5min；(1) 3mmol oxalic acid was placed in 20ml deionized water and carried out magnetic stirring for 5min, and the stirring speed was 600r/min, then the oxalic acid solution was placed in a supersonicator to carry out ultrasonic dispersion 5min;

(2)将1mmol硝酸镍、2mmol硝酸钴加入40ml甲醇中，超声5min，磁力搅拌5min，搅拌速度为600r/min，得到的粉色透明硝酸盐溶液，其中镍钴离子的摩尔比为1:2；(2) 1mmol nickel nitrate, 2mmol cobalt nitrate are added in 40ml methanol, ultrasonic 5min, magnetic stirring 5min, stirring speed is 600r/min, the pink transparent nitrate solution obtained, wherein the mol ratio of nickel-cobalt ion is 1:2;

(3)将步骤(2)配制的溶液倒入步骤(1)配制的溶液中，然后将混合溶液搅拌5min，得到前驱体溶液；(3) pour the solution prepared in step (2) into the solution prepared in step (1), then stir the mixed solution for 5min to obtain a precursor solution;

(4)将步骤(3)中所得前驱体溶液加入到高压反应釜内胆中，将内胆旋好放入高压反应釜外壳中，将高压反应釜放入鼓风干燥箱，加热到120℃，保持24h；水热反应结束后，通过离心分离沉淀物，用去离子水和乙醇分别洗涤三次，然后置于真空干燥箱中干燥，干燥温度为60℃，干燥时间为12h；(4) adding the obtained precursor solution in the step (3) into the inner liner of the autoclave, twisting the inner liner and putting it into the outer shell of the autoclave, putting the autoclave into the blast drying oven, and heating to 120° C. , kept for 24h; after the hydrothermal reaction, the precipitate was separated by centrifugation, washed three times with deionized water and ethanol, and then dried in a vacuum drying oven at a drying temperature of 60°C and a drying time of 12h;

(5)将步骤(4)中所得产物与硒粉混合置于瓷舟中，于氩气气氛下进行退火，前驱体与硒粉的摩尔比为0.5:1.2，升温速率10℃/min，退火温度为350℃，保温时间为2h，氩气流量为80sccm，随炉冷却，目的是使得硒粉升华，有利于纳米颗粒片的硒化，得到二元镍钴硒化物纳米片材料。(5) The product obtained in step (4) is mixed with selenium powder and placed in a porcelain boat, and annealed in an argon atmosphere. The molar ratio of the precursor to the selenium powder is 0.5:1.2, the heating rate is 10°C/min, and the annealing is carried out. The temperature is 350°C, the holding time is 2h, the argon gas flow is 80sccm, and the furnace is cooled to sublimate the selenium powder, which is beneficial to the selenization of the nanoparticle sheet, and obtains the binary nickel cobalt selenide nanosheet material.

本实施例制备的二元镍钴硒化物纳米片材料具有明显的硒化镍与硒化钴的相，无杂质相。本实施例的电催化性能如图7所示，在10mA/cm²的电流密度时过电势为324mV。The binary nickel cobalt selenide nanosheet material prepared in this example has obvious nickel selenide and cobalt selenide phases, and no impurity phase. The electrocatalytic performance of this example is shown in Figure 7, with an overpotential of 324 mV at a current density of 10 mA/cm² .

实施例2Example 2

(1)将3mmol草酸置于20ml去离子水中进行磁力搅拌5min，搅拌速度为700r/min，然后将草酸溶液置于超声器中进行超声分散5min；(1) 3mmol oxalic acid was placed in 20ml deionized water and carried out magnetic stirring for 5min, and the stirring speed was 700r/min, then the oxalic acid solution was placed in a supersonicator to carry out ultrasonic dispersion 5min;

(2)将1mmol硝酸镍、2mmol硝酸钴加入40ml甲醇中，超声5min，磁力搅拌5min，搅拌速度为700r/min，得到的粉色透明硝酸盐溶液，其中镍钴离子的摩尔比为1:2；(2) 1mmol nickel nitrate, 2mmol cobalt nitrate are added in 40ml methanol, ultrasonic 5min, magnetic stirring 5min, stirring speed is 700r/min, the pink transparent nitrate solution obtained, wherein the mol ratio of nickel-cobalt ion is 1:2;

(5)将步骤(4)中所得产物和硒粉与硒粉混合置于瓷舟中，于氩气气氛下进行退火，前驱体与硒粉的摩尔比为0.5:1.3，升温速率10℃/min，退火温度为350℃，保温时间为2h，氩气流量为90sccm，随炉冷却，目的是使得硒粉升华，有利于纳米颗粒片的硒化，得到二元镍钴硒化物纳米片材料。(5) The product obtained in step (4) and the selenium powder and the selenium powder are mixed and placed in a porcelain boat, and annealed in an argon atmosphere. min, the annealing temperature is 350°C, the holding time is 2h, the argon gas flow is 90sccm, and the furnace is cooled, the purpose is to sublimate the selenium powder, which is conducive to the selenization of the nanoparticle sheet, and obtain binary nickel cobalt selenide nanosheet material.

本实施例制备二元镍钴硒化物纳米片材料具有明显的硒化镍与硒化钴的相，无杂质相。图2的扫描形貌图显示出清晰的多层纳米片结构，每层纳米片长宽分别为600-700nm与200-300nm。图3-6的X射线光电子能谱图表明镍元素与钴元素的成功硒化，无杂质元素的掺入，通过拟合峰的面积占比可以看到所得材料具有高比例的Ni³⁺与Co³⁺。本实施例的电催化性能如图7所示，在10mA/cm^-2的电流密度时过电势为310mV，本实施例具有更低的析氧过电势，具有更好的析氧性能。The binary nickel-cobalt selenide nanosheet material prepared in this example has obvious phases of nickel selenide and cobalt selenide, and no impurity phase. The scanning topography of Figure 2 shows a clear multilayer nanosheet structure, and the length and width of each nanosheet are 600-700 nm and 200-300 nm, respectively. The X-ray photoelectron spectrograms in Figure 3-6 show the successful selenization of nickel and cobalt elements without the incorporation of impurity elements. By fitting the area ratio of the peaks, it can be seen that the obtained material has a high proportion of Ni³⁺ and Co³⁺ . The electrocatalytic performance of this example is shown in Fig. 7, the overpotential is 310mV at a current density of 10mA/cm^-2 , this example has lower oxygen evolution overpotential and better oxygen evolution performance.

实施例3Example 3

(1)将3mmol草酸置于20ml去离子水中进行磁力搅拌5min，搅拌速度为800r/min，然后将草酸溶液置于超声器中进行超声分散5min；(1) 3mmol oxalic acid was placed in 20ml deionized water and carried out magnetic stirring for 5min, and the stirring speed was 800r/min, and then the oxalic acid solution was placed in a supersonicator to carry out ultrasonic dispersion 5min;

(2)将1mmol硝酸镍、2mmol硝酸钴加入40ml甲醇中，超声5min，磁力搅拌5min，搅拌速度为800r/min，得到的粉色透明硝酸盐溶液，其中镍钴离子的摩尔比为1:2；(2) 1mmol nickel nitrate, 2mmol cobalt nitrate are added in 40ml methanol, ultrasonic 5min, magnetic stirring 5min, stirring speed is 800r/min, the pink transparent nitrate solution obtained, wherein the mol ratio of nickel-cobalt ion is 1:2;

(5)将步骤(4)中所得产物和硒粉与硒粉混合置于瓷舟中，于氩气气氛下进行退火，前驱体与硒粉的摩尔比为0.5:1.4，升温速率5℃/min，退火温度为350℃，保温时间为2h，氩气流量为100sccm，随炉冷却，目的是使得硒粉升华，有利于纳米颗粒片的硒化，得到二元镍钴硒化物纳米片材料。(5) The product obtained in step (4) and the selenium powder and the selenium powder are mixed and placed in a porcelain boat, and annealed in an argon atmosphere, the molar ratio of the precursor to the selenium powder is 0.5:1.4, and the heating rate is 5°C/ min, the annealing temperature is 350°C, the holding time is 2h, the argon gas flow is 100sccm, and the furnace is cooled, the purpose is to sublimate the selenium powder, which is conducive to the selenization of the nanoparticle sheet, and obtain binary nickel cobalt selenide nanosheet material.

本实施例制备二元镍钴硒化物纳米片材料具有明显的硒化镍与硒化钴的相，无杂质相。本实施例的电催化性能如图7所示，在10mA/cm²的电流密度时过电势为335mV。The binary nickel-cobalt selenide nanosheet material prepared in this example has obvious phases of nickel selenide and cobalt selenide, and no impurity phase. The electrocatalytic performance of this example is shown in Figure 7, with an overpotential of 335mV at a current density of 10mA/^cm2 .

由图1所示，五个明显的衍射峰均能与NiSe₂(JCPDS：88-1711)和CoSe₂(JCPDS：88-1712)的衍射峰相对应，表明实施例1-3成功制备了二元镍钴硒化物纳米片材料。As shown in Figure 1, the five obvious diffraction peaks can all correspond to the diffraction peaks of NiSe₂ (JCPDS: 88-1711) and CoSe₂ (JCPDS: 88-1712), indicating that Examples 1-3 successfully prepared two diffraction peaks. Nickel cobalt selenide nanosheet material.

实施例1-3制备得到的二元镍钴硒化物纳米片材料均能够应用于电化学领域；可以选择应用在电极上，具体用法如下：在室温下，将5mg二元镍钴硒化物纳米片材料样品分散到990μL乙醇中，加入10μL 5wt％的Nafion(全氟磺酸型聚合物溶液)溶液超声30min形成均一的溶液，然后将10μL混合溶液滴加到抛光的玻碳电极上，自然干燥后作得到电催化工作电极。The binary nickel-cobalt selenide nanosheet materials prepared in Examples 1-3 can all be used in the field of electrochemistry; they can be applied to electrodes, and the specific usage is as follows: at room temperature, 5 mg of binary nickel-cobalt selenide nanosheets The material sample was dispersed in 990 μL of ethanol, and 10 μL of 5wt% Nafion (perfluorosulfonic acid type polymer solution) solution was added to ultrasonic for 30 min to form a homogeneous solution, and then 10 μL of the mixed solution was added dropwise to the polished glassy carbon electrode. After natural drying An electrocatalytic working electrode was fabricated.

以上内容仅仅是对本发明结构所作的举例和说明，所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，只要不偏离本发明的结构或者超越本权利要求书所定义的范围，均应属于本发明的保护范围。The above contents are only examples and descriptions of the structure of the present invention. Those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the structure of the present invention. Or beyond the scope defined by the claims, all belong to the protection scope of the present invention.

Claims

Translated fromChinese

1.一种二元镍钴硒化物纳米片材料的制备方法，其特征在于：由水热反应制备出二元镍钴前驱体溶液，然后采用硒化退火法制备得到所述二元镍钴硒化物纳米片材料。1. a preparation method of binary nickel-cobalt selenide nanosheet material, is characterized in that: prepare binary nickel-cobalt precursor solution by hydrothermal reaction, then adopt selenization annealing method to prepare described binary nickel-cobalt-selenium Compound nanosheet materials.

2.根据权利要求1所述的一种二元镍钴硒化物纳米片材料的制备方法，其特征在于，所述水热反应具体包括以下步骤：2. the preparation method of a kind of binary nickel cobalt selenide nanosheet material according to claim 1, is characterized in that, described hydrothermal reaction specifically comprises the following steps:

3.根据权利要求2所述的一种二元镍钴硒化物纳米片材料的制备方法，其特征在于：所述步骤(1)的具体过程如下，将草酸置于去离子水中进行磁力搅拌5～10min，搅拌速度为600～800r/min，然后将草酸溶液置于超声器中进行超声分散5～10min。3. the preparation method of a kind of binary nickel cobalt selenide nanosheet material according to claim 2, is characterized in that: the concrete process of described step (1) is as follows, oxalic acid is placed in deionized water and carries out magnetic stirring 5 ~10min, the stirring speed is 600~800r/min, and then the oxalic acid solution is placed in an ultrasonicator for ultrasonic dispersion for 5~10min.

4.根据权利要求2所述的一种二元镍钴硒化物纳米片材料的制备方法，其特征在于：所述步骤(2)中，超声5～10min，磁力搅拌5～10min，搅拌速度为600～800r/min，得到的硝酸盐溶液中镍钴离子的摩尔比为1:2。4. the preparation method of a kind of binary nickel cobalt selenide nanosheet material according to claim 2, is characterized in that: in described step (2), ultrasonic 5～10min, magnetic stirring 5～10min, stirring speed is 600～800r/min, the molar ratio of nickel and cobalt ions in the obtained nitrate solution is 1:2.

5.根据权利要求2所述的一种二元镍钴硒化物纳米片材料的制备方法，其特征在于：所述草酸为3mmol，去离子水为20ml，硝酸镍为1mmol，硝酸钴为2mmol，甲醇为40ml。5. the preparation method of a kind of binary nickel cobalt selenide nanosheet material according to claim 2, is characterized in that: described oxalic acid is 3mmol, deionized water is 20ml, nickel nitrate is 1mmol, and cobalt nitrate is 2mmol, Methanol is 40ml.

6.根据权利要求2所述的一种二元镍钴硒化物纳米片材料的制备方法，其特征在于：所述步骤(1)中的去离子水与步骤(2)中的甲醇的体积比为1:2。6. the preparation method of a kind of binary nickel cobalt selenide nanosheet material according to claim 2, is characterized in that: the volume ratio of the deionized water in described step (1) and the methanol in step (2) 1:2.

7.根据权利要求1所述的一种二元镍钴硒化物纳米片材料的制备方法，其特征在于，所述硒化退火法具体包括以下步骤：7. the preparation method of a kind of binary nickel cobalt selenide nanosheet material according to claim 1, is characterized in that, described selenization annealing method specifically comprises the following steps:

8.根据权利要求7所述的一种二元镍钴硒化物纳米片材料的制备方法，其特征在于：所述步骤(1)中，水热反应后，干燥条件如下，干燥温度为55～65℃，干燥时间为10～14h。8 . The method for preparing a binary nickel-cobalt selenide nanosheet material according to claim 7 , wherein in the step (1), after the hydrothermal reaction, the drying conditions are as follows, and the drying temperature is 55 to 55 . 65 ℃, drying time is 10 ~ 14h.

9.根据权利要求7所述的一种二元镍钴硒化物纳米片材料的制备方法，其特征在于：所述步骤(2)中，煅烧温度为300～350℃，升温速率为5～10℃/min，保温时间为0.5～2h。9 . The method for preparing a binary nickel-cobalt selenide nanosheet material according to claim 7 , wherein in the step (2), the calcination temperature is 300-350° C., and the heating rate is 5-10° C. 10 . ℃/min, the holding time is 0.5～2h.

10.根据权利要求7所述的一种二元镍钴硒化物纳米片材料的制备方法，其特征在于：所述步骤(2)中，氩气流量为80～100sccm。10 . The method for preparing a binary nickel-cobalt selenide nanosheet material according to claim 7 , wherein in the step (2), the flow rate of argon gas is 80-100 sccm. 11 .