CN114807973A

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Publication number: CN114807973A
Application number: CN202210608291.7A
Authority: CN
Inventors: 彭祥; 熊礼威; 邱云帆
Original assignee: Wuhan Institute of Technology
Current assignee: Wuhan Institute of Technology
Priority date: 2022-05-31
Filing date: 2022-05-31
Publication date: 2022-07-29
Anticipated expiration: 2042-05-31
Also published as: CN114807973B

Abstract

Translated fromChinese

本发明公开了一种铈修饰的镍基催化剂及其制备方法与应用，该催化剂为负载有CeO₂的Ni₃N纳米片，其制备方法为，S1.以镍盐为原料，以导电基底作为载体，在结构导向剂的作用下，进行水热反应，得到氢氧化镍前驱体；S2.在含氮气氛下，将氢氧化镍前驱体进行煅烧，形成镍基催化剂材料；S3.将镍基催化剂材料置于含铈的电解液中，进行电沉积反应，即得铈修饰的镍基催化剂材料，可调节材料表面的活性位点数目及电子结构，具有低电阻、低能垒、高阳极催化性能及高稳定性的特性。

The invention discloses a cerium-modified nickel-based catalyst and a preparation method and application thereof. The catalyst is Ni₃ N nanosheets loaded with CeO₂ , and the preparation method is as follows: S1. The carrier, under the action of the structure-directing agent, undergoes a hydrothermal reaction to obtain a nickel hydroxide precursor; S2. In a nitrogen-containing atmosphere, the nickel hydroxide precursor is calcined to form a nickel-based catalyst material; S3. The nickel-based catalyst material is formed. The catalyst material is placed in a cerium-containing electrolyte and undergoes an electrodeposition reaction to obtain a cerium-modified nickel-based catalyst material, which can adjust the number of active sites and electronic structure on the surface of the material, and has low resistance, low energy barrier, and high anode catalytic performance. and high stability characteristics.

Description

Translated fromChinese

一种铈修饰的镍基催化剂及其制备方法与应用A kind of cerium-modified nickel-based catalyst and its preparation method and application

技术领域technical field

本发明涉及纳米材料技术领域，尤其是涉及一种铈修饰的镍基催化剂及其制备方法与应用。The invention relates to the technical field of nanomaterials, in particular to a cerium-modified nickel-based catalyst and a preparation method and application thereof.

背景技术Background technique

传统的化石燃料仍然是能源的主要提供对象，但是化石燃料的燃烧带来的环境问题严重影响了地球的环境，因此，科学家们致力于寻找可再生的清洁燃料来取代化石燃料，由于氢燃烧后的产物只有水，将氢作为汽车的能源可以杜绝尾气中二氧化碳的排放。为了合理高效地开发和利用氢能，氢能的生产和转换成为了近年来科学家们研究的热点问题。电催化分解水被认为是一种能够生产高纯度氢的最快速、最安全、最绿色的可持续方法，同时也被视为一种大规模储能的间接方式。Traditional fossil fuels are still the main source of energy, but the environmental problems brought about by the burning of fossil fuels have seriously affected the earth's environment. Therefore, scientists are committed to finding renewable and clean fuels to replace fossil fuels. The product is only water, and using hydrogen as an energy source for cars can eliminate carbon dioxide emissions in the exhaust. In order to develop and utilize hydrogen energy reasonably and efficiently, the production and conversion of hydrogen energy has become a hot research topic of scientists in recent years. Electrocatalytic water splitting is considered to be the fastest, safest, and greenest sustainable method capable of producing high-purity hydrogen, and is also seen as an indirect means of large-scale energy storage.

氢能作为二次能源，它的制取不但需要消耗大量的能量，而且制备的氢气效率很低，而电解水产氢由于可持续性和操作简易的特点，被认为是一种实用的无污染制氢方法，受到了广泛的关注。阴极上的析氢反应(HER)和阳极上的析氧反应(OER)的水电解对水转化为氢起着重要作用。通过催化剂的作用可有效的降低反应所需的过电势，从而提升产氢效率。Hydrogen energy is a secondary energy source. Its production not only consumes a lot of energy, but also produces hydrogen with low efficiency. Hydrogen production from water electrolysis is considered to be a practical non-polluting system due to its sustainability and ease of operation. The hydrogen method has received extensive attention. Water electrolysis by hydrogen evolution reaction (HER) at the cathode and oxygen evolution reaction (OER) at the anode plays an important role in the conversion of water to hydrogen. The overpotential required for the reaction can be effectively reduced by the action of the catalyst, thereby improving the hydrogen production efficiency.

在电催化水分解反应中，常见催化剂由Pt、Ru、Ir贵金属及其合金和化合物组成，但成本高和自然稀缺性阻碍了更广泛的应用，因此亟需开发经济、稳定、高效的新型催化剂。近年来，随着电催化领域的快速出现，非贵金属催化剂如过渡金属硫族化物、氮化物、碳化物、硒化物、磷化物，为这一领域带来了新的机遇。In electrocatalytic water splitting reactions, common catalysts are composed of Pt, Ru, Ir noble metals and their alloys and compounds, but high cost and natural scarcity hinder wider applications, so there is an urgent need to develop economical, stable, and efficient new catalysts . In recent years, with the rapid emergence of the field of electrocatalysis, non-noble metal catalysts such as transition metal chalcogenides, nitrides, carbides, selenides, and phosphides have brought new opportunities to this field.

然而上述非金属催化剂在电催化水分解反应中，产氢效率常常受到阳极反应的较慢的动力学过程的限制，从而影响了整体的产氢效率。However, in the electrocatalytic water splitting reaction of the above-mentioned non-metallic catalysts, the hydrogen production efficiency is often limited by the slower kinetic process of the anode reaction, thus affecting the overall hydrogen production efficiency.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于，提供一种铈修饰的镍基催化剂及其制备方法与应用，提升了电解水的效率。The purpose of the present invention is to provide a cerium-modified nickel-based catalyst and a preparation method and application thereof, which improve the efficiency of electrolysis of water.

为达到上述技术目的，本申请采用以下技术方案：In order to achieve the above-mentioned technical purpose, the application adopts the following technical solutions:

第一方面，本申请提供一种铈修饰的镍基催化剂材料，其为负载有CeO₂的Ni₃N纳米片。In a first aspect, the present application provides a cerium-modified nickel-based catalyst material, which is Ni₃ N nanosheets loaded with CeO₂ .

第二方面，本申请提供一种铈修饰的镍基催化剂材料的制备方法，包括以下步骤：In a second aspect, the present application provides a method for preparing a cerium-modified nickel-based catalyst material, comprising the following steps:

S1.以镍盐为原料，以导电基底作为载体，在结构导向剂的作用下，进行水热反应，得到氢氧化镍前驱体；S1. Using nickel salt as raw material, using conductive substrate as carrier, under the action of structure directing agent, hydrothermal reaction is carried out to obtain nickel hydroxide precursor;

S2.在含氮气氛下，将氢氧化镍前驱体进行煅烧，形成镍基催化剂材料；S2. calcining the nickel hydroxide precursor in a nitrogen-containing atmosphere to form a nickel-based catalyst material;

S3.将镍基催化剂材料置于含铈的电解液中，进行电沉积反应，即得铈修饰的镍基催化剂材料。S3. The nickel-based catalyst material is placed in an electrolyte solution containing cerium, and an electrodeposition reaction is performed to obtain a cerium-modified nickel-based catalyst material.

优选的，结构导向剂为尿素及氟化铵的混合物。Preferably, the structure directing agent is a mixture of urea and ammonium fluoride.

优选的，镍盐、尿素、氟化铵的摩尔比为1-4:5-10:2-5。Preferably, the molar ratio of nickel salt, urea and ammonium fluoride is 1-4:5-10:2-5.

优选的，镍盐包括硝酸镍、氯化镍、磷化镍、溴化镍、硫酸镍的一种或几种。Preferably, the nickel salt includes one or more of nickel nitrate, nickel chloride, nickel phosphide, nickel bromide, and nickel sulfate.

优选的，含铈的电解液包括硝酸铈溶液、氯化铈溶液、硫酸铈溶液中的一种或几种。Preferably, the cerium-containing electrolyte includes one or more of a cerium nitrate solution, a cerium chloride solution, and a cerium sulfate solution.

优选的，步骤S1中，水热反应的反应温度为90-200℃，反应时间为4-24h。Preferably, in step S1, the reaction temperature of the hydrothermal reaction is 90-200° C., and the reaction time is 4-24 h.

优选的，步骤S2中，煅烧的升温速率为1-25℃/min，终温为150-700℃，保温时间为20-360min。Preferably, in step S2, the heating rate of calcination is 1-25°C/min, the final temperature is 150-700°C, and the holding time is 20-360min.

优选的，步骤S3中，电沉积反应的电压为0.05-10V，反应时间为1-30h。Preferably, in step S3, the voltage of the electrodeposition reaction is 0.05-10V, and the reaction time is 1-30h.

第三方面，本申请提供一种铈修饰的镍基催化剂材料作为阳极电极在电催化析氧中的应用。In a third aspect, the present application provides an application of a cerium-modified nickel-based catalyst material as an anode electrode in electrocatalytic oxygen evolution.

本发明的有益效果是：The beneficial effects of the present invention are:

1.通过水热法、化学气相沉积以及电沉积技术结合，在氮化镍纳米片上沉积铈元素得到铈修饰的镍基催化剂材料，可调节材料表面的活性位点数目及电子结构，具有低电阻、低能垒、高阳极催化性能及高稳定性的特性；1. Through the combination of hydrothermal method, chemical vapor deposition and electrodeposition technology, cerium element is deposited on nickel nitride nanosheets to obtain a cerium-modified nickel-based catalyst material, which can adjust the number of active sites and electronic structure on the surface of the material, and has low resistance , low energy barrier, high anode catalytic performance and high stability;

2.本申请得到的铈修饰的镍基催化剂材料增加了析氧反应中的催化剂的活性及材料的电子传输性能，促进动力学过程的发生，提升电解水效率；2. The cerium-modified nickel-based catalyst material obtained in the present application increases the activity of the catalyst in the oxygen evolution reaction and the electron transport performance of the material, promotes the occurrence of kinetic processes, and improves the efficiency of water electrolysis;

3.本申请的制备工艺简单、成本低廉，适用于大规模生产。3. The preparation process of the present application is simple and low in cost, and is suitable for large-scale production.

附图说明Description of drawings

图1为不同电催化材料的析氧极化曲线图。Figure 1 shows the oxygen evolution polarization curves of different electrocatalytic materials.

图2为不同电催化材料的阻抗曲线图。Figure 2 is a graph of impedance curves of different electrocatalytic materials.

具体实施方式Detailed ways

下面将结合本发明实施例，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，均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 embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all 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.

已为普遍意识到的是，非贵金属催化剂如过渡金属硫族化物、氮化物、碳化物、硒化物、磷化物可作为电催化水分解析氧反应的催化剂，但是由于这类催化剂材料能类垒较高、动力学反应过程慢，因此使得电解水的效率降低，而通过非金属的掺杂配合，能改善材料内部的电阻，降低阳极反应所需的能垒，以促进整个动力学过程及产氢过程的发生，特别是氮元素的存在，可对材料的晶格起到调节作用，可增大晶格的畸变程度，促进氢离子的吸附和剥离，降低反应能垒，使催化活性得到增强，电解水效率增高，基于此，创立了本申请。It has been generally recognized that non-noble metal catalysts such as transition metal chalcogenides, nitrides, carbides, selenides, phosphides can be used as catalysts for electrocatalytic water-separation oxygen reactions, but due to the relatively low energy class barriers of such catalyst materials. High, slow kinetic reaction process, thus reducing the efficiency of water electrolysis, and through the doping of non-metals, the internal resistance of the material can be improved, and the energy barrier required for the anode reaction can be reduced to promote the entire kinetic process and hydrogen production. The occurrence of the process, especially the presence of nitrogen, can adjust the lattice of the material, increase the degree of lattice distortion, promote the adsorption and exfoliation of hydrogen ions, reduce the reaction energy barrier, and enhance the catalytic activity. The present application was created based on the increased efficiency of electrolysis of water.

本申请的实施例提供一种铈修饰的镍基催化剂材料，其为负载有CeO₂的Ni₃N纳米片，通过铈的修饰降低材料内部的电阻，降低阳极反应所需的能垒，从而促进整个动力学过程的发生，提升了电解水的催化性能。The embodiments of the present application provide a cerium-modified nickel-based catalyst material, which is Ni₃ N nanosheets loaded with CeO₂ . The modification of cerium reduces the internal resistance of the material and reduces the energy barrier required for the anode reaction, thereby promoting The occurrence of the entire kinetic process improves the catalytic performance of electrolyzed water.

在先技术人员对于镍基催化剂材料的修饰存在稳定性差的技术困难，因此负载的修饰材料少、易于脱落，也使得被修饰的镍基催化剂材料在电解水过程中效率有待提升，而本申请中，提供一种铈修饰的镍基催化剂材料的制备方法，包括以下步骤：The modification of nickel-based catalyst materials by prior technicians has technical difficulties with poor stability. Therefore, the supported modification materials are few and easy to fall off, which also makes the efficiency of the modified nickel-based catalyst materials in the process of electrolysis of water to be improved. In the present application , a preparation method of a cerium-modified nickel-based catalyst material is provided, comprising the following steps:

S1.以镍盐为原料，以导电基底作为载体，在以尿素和氟化铵作为结构导向剂，进行水热反应，得到氢氧化镍前驱体；S1. use nickel salt as raw material, use conductive substrate as carrier, and use urea and ammonium fluoride as structure-directing agent to carry out hydrothermal reaction to obtain nickel hydroxide precursor;

S2.在含氮气氛下，将氢氧化镍前驱体进行煅烧，形成镍基催化剂材料即负载有氮化镍的导电基底；S2. In a nitrogen-containing atmosphere, the nickel hydroxide precursor is calcined to form a nickel-based catalyst material, that is, a conductive substrate loaded with nickel nitride;

上述方法中，镍盐通过水热法在高温高压的条件，经溶解及再结晶过程在导电基底上制得含氢氧化镍前驱体，再经化学气相沉积法使前驱体在氮气气氛中发生反应得到氮化镍纳米片，而电沉积技术则在电流的作用下使铈元素扩散至纳米片表面，与氮化镍相结合形成铈修饰的镍基催化剂材料。In the above method, a nickel hydroxide-containing precursor is prepared on a conductive substrate through a process of dissolution and recrystallization of the nickel salt under the condition of high temperature and high pressure by a hydrothermal method, and then the precursor is reacted in a nitrogen atmosphere by a chemical vapor deposition method. Nickel nitride nanosheets are obtained, and the electrodeposition technology makes cerium element diffuse to the surface of the nanosheets under the action of electric current, and combines with nickel nitride to form a cerium modified nickel-based catalyst material.

本申请中，以尿素及氟化铵为结构导向剂，用于控制前驱体的形貌，形成不规则纳米片结构，并在高温高压的作用下沉降附着在导电基底上，在尿素和氟化铵的作用下保持纳米片形貌，形成氢氧化镍前驱体，氢氧化镍前驱体使纳米片结构更加稳定，更适合铈氧化物的生长与复合，提高了催化材料的稳定性，同时调节了材料表面的活性位点数目及电子结构，增加了析氧反应中的催化剂的活性，增强了材料的电子传输性能，因此电解水的效率得以提高。In this application, urea and ammonium fluoride are used as structure-directing agents to control the morphology of the precursor to form an irregular nanosheet structure, which settles and attaches to the conductive substrate under the action of high temperature and high pressure. Under the action of ammonium, the morphology of the nanosheets is maintained, and a nickel hydroxide precursor is formed. The nickel hydroxide precursor makes the nanosheet structure more stable, more suitable for the growth and compounding of cerium oxide, and improves the stability of the catalytic material. The number of active sites and electronic structure on the surface of the material increase the activity of the catalyst in the oxygen evolution reaction, enhance the electron transport performance of the material, and thus improve the efficiency of water electrolysis.

本申请中，镍盐为含过渡金属镍的阳离子溶液，包括硝酸镍、氯化镍、磷化镍、溴化镍或硫酸镍中的一种或几种，进一步的，镍盐为氯化镍。In this application, the nickel salt is a cation solution containing transition metal nickel, including one or more of nickel nitrate, nickel chloride, nickel phosphide, nickel bromide or nickel sulfate, and further, the nickel salt is nickel chloride .

本申请中，含铈的电解液包括硝酸铈溶液、氯化铈溶液、硫酸铈溶液中的一种或几种。In this application, the cerium-containing electrolyte includes one or more of a cerium nitrate solution, a cerium chloride solution, and a cerium sulfate solution.

在一些实施例中，镍盐、尿素、氟化铵的摩尔比为1-4:5-10:2-5，如1:5:2、1:7:3、4:10:5，但不限于所列举的数值，该数值范围内未列举的数值同样适用。In some embodiments, the molar ratio of nickel salt, urea, and ammonium fluoride is 1-4:5-10:2-5, such as 1:5:2, 1:7:3, 4:10:5, but Without being limited to the recited numerical values, non-recited numerical values within the numerical range also apply.

将电催化材料与导电基底进行整合通常可改善其性能和稳定性，这是由于将电催化剂直接与导电基底复合确保了电子传输通路阻抗较低并减少了电催化剂物理分层的可能性，导电基底和电催化剂之间的电子耦合可以协同提高内在活性，本申请中，导电基底包括碳布、纤维纸、泡沫镍、泡沫铜等其中的一种，进一步的，导电基底为碳布。Integrating electrocatalytic materials with conductive substrates generally improves their performance and stability, as direct compounding of the electrocatalyst with the conductive substrate ensures low electron transport path impedance and reduces the potential for physical delamination of the electrocatalyst, which is conductive. The electronic coupling between the substrate and the electrocatalyst can synergistically improve the intrinsic activity. In this application, the conductive substrate includes one of carbon cloth, fiber paper, foamed nickel, and foamed copper. Further, the conductive substrate is carbon cloth.

本申请中，含氮气氛指的是含有氮元素的气氛，包括氨气、氮气、氮气与氩气混合气等其中的一种，进一步的，氮气气氛为氮气，含氮气氛为反应提供氮源，使前驱体氢氧化镍中的镍元素与氮元素发生化学反应，得到氮化镍。In this application, nitrogen-containing atmosphere refers to an atmosphere containing nitrogen elements, including one of ammonia, nitrogen, and a mixture of nitrogen and argon. Further, the nitrogen-containing atmosphere is nitrogen, and the nitrogen-containing atmosphere provides a nitrogen source for the reaction , the nickel element in the precursor nickel hydroxide is chemically reacted with the nitrogen element to obtain nickel nitride.

在一些具体的实施例中，步骤S1中，水热反应的反应温度为90-200℃，例如90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃，但不限于所列举的数值，该数值范围内未列举的数值同样适用，水热反应时间为4-24h，例如4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h，但不限于所列举的数值，该数值范围内未列举的数值同样适用。In some specific embodiments, in step S1, the reaction temperature of the hydrothermal reaction is 90-200°C, such as 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C ℃, 180 ℃, 190 ℃, 200 ℃, but not limited to the listed values, the values not listed in the numerical range are also applicable, the hydrothermal reaction time is 4-24h, such as 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, but not limited to the listed values, and the values not listed in the numerical range are also applicable.

本申请中，煅烧的过程是将氢氧化镍前驱体进行气相沉积的过程，其具体手段是通过一定速率升温至终温后，保温一段时间，在一些具体的实施例中，步骤S2中，煅烧的升温速率为1-25℃/min，例如1℃/min、2℃/min、3℃/min、4℃/min、5℃/min、6℃/min、7℃/min、8℃/min、9℃/min、10℃/min、11℃/min、12℃/min、13℃/min、14℃/min、15℃/min、16℃/min、17℃/min、18℃/min、19℃/min、20℃/min、21℃/min、22℃/min、23℃/min、24℃/min、25℃/min，但不限于所列举的数值，该数值范围内未列举的数值同样适用，终温为150-700℃，例如150℃、200℃、250℃、300℃、350℃、400℃、450℃、500℃、550℃、600℃、650℃、700℃，但不限于所列举的数值，该数值范围内未列举的数值同样适用，保温时间为20-360min，例如20min、40min、60min、100min、150min、200min、250min、360min，但不限于所列举的数值，该数值范围内未列举的数值同样适用，如本文，“终温”是指氢氧化镍前驱体进行气相沉积的最终反应温度，“保温时间”是指氢氧化镍前驱体进行气相沉积的反应时间。In the present application, the calcination process is the process of vapor deposition of nickel hydroxide precursor. The specific method is to heat up to the final temperature at a certain rate, and keep it for a period of time. In some specific embodiments, in step S2, calcination The heating rate is 1-25°C/min, such as 1°C/min, 2°C/min, 3°C/min, 4°C/min, 5°C/min, 6°C/min, 7°C/min, 8°C/min min, 9℃/min, 10℃/min, 11℃/min, 12℃/min, 13℃/min, 14℃/min, 15℃/min, 16℃/min, 17℃/min, 18℃/min min, 19°C/min, 20°C/min, 21°C/min, 22°C/min, 23°C/min, 24°C/min, 25°C/min, but not limited to the listed values, no The values listed also apply, the final temperature is 150-700°C, for example 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C , but not limited to the listed values, the values not listed in the numerical range are also applicable, the holding time is 20-360min, such as 20min, 40min, 60min, 100min, 150min, 200min, 250min, 360min, but not limited to the listed Numerical values, the numerical values not listed in the numerical range are also applicable, as in this paper, "final temperature" refers to the final reaction temperature of the nickel hydroxide precursor for vapor deposition, and "holding time" refers to the nickel hydroxide precursor for vapor deposition. Reaction time.

在一些具体的实施例中，步骤S3中，电沉积反应的电压为0.05-10V，例如0.05V、0.1V、0.5V、1V、2V、4V、6V、8V、10V，但不限于所列举的数值，该数值范围内未列举的数值同样适用，反应时间为1-30h，例如1h、5h、10h、20h、25h、30h，但不限于所列举的数值，该数值范围内未列举的数值同样适用。In some specific embodiments, in step S3, the voltage of the electrodeposition reaction is 0.05-10V, such as 0.05V, 0.1V, 0.5V, 1V, 2V, 4V, 6V, 8V, 10V, but not limited to the listed ones Numerical value, the numerical value not enumerated in this numerical value range is also applicable, the reaction time is 1-30h, for example 1h, 5h, 10h, 20h, 25h, 30h, but not limited to the numerical value enumerated, the numerical value not enumerated in this numerical value range is the same Be applicable.

参照下面的实施例对本发明进行更详细地说明。The present invention is explained in more detail with reference to the following examples.

实施例1Example 1

一种铈修饰的镍基催化剂材料，其为负载有CeO₂的Ni₃N纳米片，制备方法如下：A cerium-modified nickel-based catalyst material is a Ni₃ N nanosheet loaded with CeO₂ , and the preparation method is as follows:

S1.将1mmol/L的硝酸镍、5mmol/L的尿素和2mmol的氟化铵溶解在35ml去离子水中，搅拌30min，将泡沫镍浸入上述混合溶液中，加热至120℃反应6h，反应后取出泡沫镍用去离子水洗涤3次后干燥，得到氢氧化镍前驱体。S1. Dissolve 1mmol/L nickel nitrate, 5mmol/L urea and 2mmol ammonium fluoride in 35ml deionized water, stir for 30min, immerse nickel foam in the above mixed solution, heat to 120°C for reaction for 6h, take out after reaction The nickel foam was washed three times with deionized water and then dried to obtain a nickel hydroxide precursor.

S2.将所得氢氧化镍前驱体放置在瓷舟上，并放进管式炉中，通入氨气后煅烧，得到镍基催化剂材料，其中升温速率为5℃/min，反应温度为300℃，保温时间为30min。S2. The obtained nickel hydroxide precursor is placed on a porcelain boat, and placed in a tube furnace, and then calcined after passing in ammonia gas to obtain a nickel-based catalyst material, wherein the heating rate is 5°C/min, and the reaction temperature is 300°C , the holding time is 30min.

S3.将所得镍基催化剂材料置于硫酸铈电解液中，在三电极系统中反应，得到铈修饰的镍基催化剂材料，其中反应电压为0.5V，反应时间为5h。S3. The obtained nickel-based catalyst material is placed in a cerium sulfate electrolyte, and reacted in a three-electrode system to obtain a cerium-modified nickel-based catalyst material, wherein the reaction voltage is 0.5V, and the reaction time is 5h.

实施例2Example 2

S1.将2mmol/L的硫酸镍、7mmol/L的尿素和3mmol的氟化铵溶解在28ml去离子水中，搅拌60min，将碳布浸入溶液中，加热至100℃反应8h，反应后取出碳布用去离子水洗涤3次后干燥，得到氢氧化镍前驱体；S1. Dissolve 2mmol/L of nickel sulfate, 7mmol/L of urea and 3mmol of ammonium fluoride in 28ml of deionized water, stir for 60min, immerse the carbon cloth in the solution, heat to 100°C for 8h reaction, take out the carbon cloth after the reaction Wash with deionized water for 3 times and then dry to obtain nickel hydroxide precursor;

S2.将所得氢氧化镍前驱体放置在瓷舟上，并放进管式炉中，通入氮气后煅烧，得到镍基催化剂材料，其中升温速率为10℃/min，反应温度为400℃，保温时间为60min；S2. the obtained nickel hydroxide precursor is placed on a porcelain boat, and placed in a tube furnace, and calcined after being introduced into nitrogen to obtain a nickel-based catalyst material, wherein the heating rate is 10 ℃/min, and the reaction temperature is 400 ℃, The holding time is 60min;

S3.将所得镍基催化剂材料置于硝酸铈电解液中，在三电极系统中反应，得到铈修饰的镍基催化剂材料，其中反应电压为0.7V，反应时间为9h。S3. The obtained nickel-based catalyst material is placed in a cerium nitrate electrolyte and reacted in a three-electrode system to obtain a cerium-modified nickel-based catalyst material, wherein the reaction voltage is 0.7V and the reaction time is 9h.

实施例3Example 3

S1.将4mmol/L的溴化镍、10mmol/L的尿素和5mmol的氟化铵溶解在40ml去离子水中，搅拌30min，将泡沫镍浸入溶液中，加热至150℃反应12h。反应后取出泡沫镍用去离子水洗涤3次后干燥，得到氢氧化镍前驱体；S1. Dissolve 4 mmol/L of nickel bromide, 10 mmol/L of urea and 5 mmol of ammonium fluoride in 40 ml of deionized water, stir for 30 min, immerse the nickel foam in the solution, and heat to 150 °C for 12 h. After the reaction, the nickel foam is taken out and washed with deionized water for 3 times and then dried to obtain a nickel hydroxide precursor;

S2.将所得氢氧化镍前驱体放置在瓷舟上，并放进管式炉中，通入氨气后煅烧，得到镍基催化剂材料，其中升温速率为15℃/min，反应温度为450℃，保温时间为120min。S2. The obtained nickel hydroxide precursor is placed on a porcelain boat, and placed in a tube furnace, and calcined after feeding into ammonia gas to obtain a nickel-based catalyst material, wherein the heating rate is 15°C/min, and the reaction temperature is 450°C , the holding time is 120min.

S3.将所得镍基催化剂材料置于氯化铈电解液中，在三电极系统中反应，得到铈修饰的镍基催化剂材料，其中反应电压为0.9V，反应时间为12h。S3. The obtained nickel-based catalyst material is placed in a cerium chloride electrolyte and reacted in a three-electrode system to obtain a cerium-modified nickel-based catalyst material, wherein the reaction voltage is 0.9V and the reaction time is 12h.

实施例4Example 4

一种铈修饰的镍基催化剂材料，其为负载有CeO₂的Ni₃N纳米片，其制备步骤与实施例1大体相同，所不同的是，步骤S1中，加热温度为90℃，反应时间为24h，步骤S2中，升温速率为1℃/min，反应温度为150℃，保温见识为360min，步骤S3中，反应电压为0.05V，反应时间为30h。A cerium-modified nickel-based catalyst material is Ni₃ N nanosheets loaded with CeO₂ . The preparation steps are basically the same as those in Example 1, except that in step S1, the heating temperature is 90° C., and the reaction time is 90°C. For 24h, in step S2, the heating rate is 1°C/min, the reaction temperature is 150°C, and the heat preservation knowledge is 360min. In step S3, the reaction voltage is 0.05V, and the reaction time is 30h.

实施例5Example 5

一种铈修饰的镍基催化剂材料，其为负载有CeO₂的Ni₃N纳米片，其制备步骤与实施例1大体相同，所不同的是，步骤S1中，加热温度为200℃，反应时间为4h，步骤S2中，升温速率为25℃/min，反应温度为700℃，保温见识为20min，步骤S3中，反应电压为10V，反应时间为1h。A cerium-modified nickel-based catalyst material, which is Ni₃ N nanosheets loaded with CeO₂ , the preparation steps are basically the same as those in Example 1, the difference is that in step S1, the heating temperature is 200 ° C, and the reaction time is For 4h, in step S2, the heating rate is 25°C/min, the reaction temperature is 700°C, and the heat preservation knowledge is 20min. In step S3, the reaction voltage is 10V, and the reaction time is 1h.

对比例1Comparative Example 1

一种镍基催化剂材料，其制备步骤与实施例1大体相同，所不同的是，不包括步骤S3。A nickel-based catalyst material, the preparation steps of which are substantially the same as those in Example 1, the difference is that step S3 is not included.

测试例test case

将实施例1中所制备得到的铈修饰的镍基催化剂材料与对比例1中的镍基催化剂材料进行了线性扫描伏安法(LSV)测试，测试在CHI660e的电化学工作站上进行，用三电极系统进行测试，本实施例制备的铈修饰的镍基催化剂材料电极为工作电极，Hg/HgCl₂为参比电极，石墨棒为对电极，电解液为1MKOH,HER和OER的极化曲线测试扫速为5mV s^-1。所用电压和可逆氢电极之间的换算公式为ERHE＝EHg/HgCl₂+0.0591pH+0.242；图1为本发明实施例铈修饰的镍基催化剂材料及纯氮化镍电催化材料的析氧极化曲线图，由图可得纯氮化镍催化剂需要1.86V的电压来驱动反应达到100mA cm^-2的电流密度，而铈修饰的镍基催化剂仅需1.67V的电压，所需的能量更少，可以使整体反应更好地达到理想的效果，说明本方案制备的铈修饰的镍基催化剂材料析氧性能更好。The cerium-modified nickel-based catalyst material prepared in Example 1 and the nickel-based catalyst material in Comparative Example 1 were tested by linear sweep voltammetry (LSV), and the test was carried out on an electrochemical workstation of CHI660e. The electrode system is tested. The cerium-modified nickel-based catalyst material electrode prepared in this example is the working electrode, Hg/HgCl₂ is the reference electrode, the graphite rod is the counter electrode, and the electrolyte is 1MKOH. The polarization curve test of HER and OER The sweep rate was 5mV s^-1 . The conversion formula between the voltage used and the reversible hydrogen electrode is ERHE=EHg/HgCl₂ +0.0591pH+0.242; Figure 1 shows the oxygen evolution electrode of the cerium-modified nickel-based catalyst material and the pure nickel nitride electrocatalytic material according to the embodiment of the present invention From the graph, it can be seen that the pure nickel nitride catalyst needs a voltage of 1.86V to drive the reaction to a current density of 100mA cm^-2 , while the cerium-modified nickel-based catalyst only needs a voltage of 1.67V, which requires less energy , the overall reaction can better achieve the desired effect, indicating that the cerium-modified nickel-based catalyst material prepared in this scheme has better oxygen evolution performance.

将实施例1中所制备得到的铈修饰的镍基催化剂材料与对比例1中的镍基催化剂材料进行电化学阻抗测试，依然采用三电极系统进行测试，电化学阻抗的测试(EIS)主要用来探究电极反应动力学以及电极和电解液之间的界面效应。测试过程中，给电极体系施加的恒定电压为1.6V，频率范围为0.1至100000Hz，不同频率的小正弦波扰动信号转化为相应的电化学信号。通过对阻抗图的分析，可以比较不同催化剂的反应动力学快慢。结果如图2所示，图中半径的大小代表催化剂内阻的大小，半径越小内阻越小，说明本方案制备的铈修饰的镍基催化剂材料比纯氮化镍具有更小的电荷传输电阻，能够使反应更快地发生，更利于促进反应动力学。The cerium-modified nickel-based catalyst material prepared in Example 1 and the nickel-based catalyst material in Comparative Example 1 were subjected to electrochemical impedance testing, and the three-electrode system was still used for testing. The electrochemical impedance test (EIS) was mainly used. to investigate the kinetics of electrode reactions and the interfacial effects between electrodes and electrolytes. During the test, the constant voltage applied to the electrode system was 1.6V, the frequency range was 0.1 to 100000Hz, and the small sine wave disturbance signals of different frequencies were converted into corresponding electrochemical signals. By analyzing the impedance diagram, the reaction kinetics of different catalysts can be compared. The results are shown in Figure 2. The radius in the figure represents the internal resistance of the catalyst. The smaller the radius, the smaller the internal resistance, indicating that the cerium-modified nickel-based catalyst material prepared in this scheme has smaller charge transport than pure nickel nitride. The resistance can make the reaction happen faster and is more conducive to promoting the reaction kinetics.

需要说明的是，以上各实施例均属于同一发明构思，各实施例的描述各有侧重，在个别实施例中描述未详尽之处，可参考其他实施例中的描述。It should be noted that the above embodiments all belong to the same inventive concept, and the description of each embodiment has its own emphasis. For details not described in individual embodiments, reference may be made to descriptions in other embodiments.

以上实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above examples only represent the embodiments of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as a limitation on the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can also be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims

Translated fromChinese

1.一种铈修饰的镍基催化剂材料，其特征在于，其为负载有CeO₂的Ni₃N纳米片。1. A cerium-modified nickel-based catalyst material, characterized in that it is a Ni₃ N nanosheet loaded with CeO₂ .

2.一种如权利要求1所述的铈修饰的镍基催化剂材料的制备方法，其特征在于，包括以下步骤：2. the preparation method of the nickel-based catalyst material of cerium modification as claimed in claim 1, is characterized in that, comprises the following steps:

S2.在含氮气氛下，将所述氢氧化镍前驱体进行煅烧，形成镍基催化剂材料；S2. in a nitrogen-containing atmosphere, calcining the nickel hydroxide precursor to form a nickel-based catalyst material;

S3.将所述镍基催化剂材料置于含铈的电解液中，进行电沉积反应，即得所述铈修饰的镍基催化剂材料。S3. The nickel-based catalyst material is placed in an electrolyte solution containing cerium, and an electrodeposition reaction is performed to obtain the cerium-modified nickel-based catalyst material.

3.根据权利要求2所述的铈修饰的镍基催化剂材料的制备方法，其特征在于，所述结构导向剂为尿素及氟化铵的混合物。3 . The method for preparing a cerium-modified nickel-based catalyst material according to claim 2 , wherein the structure-directing agent is a mixture of urea and ammonium fluoride. 4 .

4.根据权利要求3所述的铈修饰的镍基催化剂材料的制备方法，其特征在于，镍盐、尿素、氟化铵的摩尔比为1-4:5-10:2-5。4 . The method for preparing a cerium-modified nickel-based catalyst material according to claim 3 , wherein the molar ratio of nickel salt, urea and ammonium fluoride is 1-4:5-10:2-5. 5 .

5.根据权利要求2所述的铈修饰的镍基催化剂材料的制备方法，其特征在于，所述镍盐包括氯化镍、硫酸镍、硝酸镍中的一种或几种。5 . The method for preparing a cerium-modified nickel-based catalyst material according to claim 2 , wherein the nickel salt comprises one or more of nickel chloride, nickel sulfate, and nickel nitrate. 6 .

6.根据权利要求2所述的铈修饰的镍基催化剂材料的制备方法，其特征在于，所述含铈的电解液包括硝酸铈溶液、氯化铈溶液、硫酸铈溶液中的一种或几种。6. the preparation method of the nickel-based catalyst material modified by cerium according to claim 2, is characterized in that, described cerium-containing electrolyte comprises one or more in cerium nitrate solution, cerium chloride solution, cerium sulfate solution kind.

7.根据权利要求2所述的铈修饰的镍基催化剂材料的制备方法，其特征在于，步骤S1中，水热反应的反应温度为90-200℃，反应时间为4-24h。7 . The method for preparing a cerium-modified nickel-based catalyst material according to claim 2 , wherein in step S1 , the reaction temperature of the hydrothermal reaction is 90-200° C., and the reaction time is 4-24 h. 8 .

8.根据权利要求2所述的铈修饰的镍基催化剂材料的制备方法，其特征在于，步骤S2中，煅烧的升温速率为1-25℃/min，终温为150-700℃，保温时间为20-360min。8. The method for preparing a cerium-modified nickel-based catalyst material according to claim 2, wherein in step S2, the heating rate of calcination is 1-25°C/min, the final temperature is 150-700°C, and the holding time is 1-25°C. For 20-360min.

9.根据权利要求2所述的铈修饰的镍基催化剂材料的制备方法，其特征在于，步骤S3中，电沉积反应的电压为0.05-10V，反应时间为1-30h。9 . The method for preparing a cerium-modified nickel-based catalyst material according to claim 2 , wherein, in step S3 , the voltage of the electrodeposition reaction is 0.05-10V, and the reaction time is 1-30h. 10 .

10.一种如权利要求2-9任一项所述制备方法得到的铈修饰的镍基催化剂材料作为阳极电极在电催化析氧中的应用。10 . The application of a cerium-modified nickel-based catalyst material obtained by the preparation method according to any one of claims 2 to 9 as an anode electrode in electrocatalytic oxygen evolution. 11 .