CN115627493A - Platinum-doped catalyst electrode and preparation method and application thereof - Google Patents
Platinum-doped catalyst electrode and preparation method and application thereofDownload PDFInfo
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Abstract
Translated fromChinese
Description
Translated fromChinese技术领域technical field
本发明属于电催化剂技术领域，具体涉及一种铂掺杂催化剂电极及其制备方法和应用。The invention belongs to the technical field of electrocatalysts, and in particular relates to a platinum-doped catalyst electrode and its preparation method and application.
背景技术Background technique
随着社会的快速发展，能源短缺越来越严峻，对新能源的探索与研究迫在眉睫。太阳能、风能等环境友好型清洁能源研究基础雄厚，但这些能源的使用受到季节性、地域性、波动性等外界因素的严重制约。氢能源由于其燃烧热值高、来源广和无污染等特点，作为一种二次能源存储能量有极其广阔的应用前景。With the rapid development of society, the energy shortage is becoming more and more serious, and the exploration and research of new energy sources are imminent. The research foundation of environmentally friendly clean energy such as solar energy and wind energy is solid, but the use of these energy sources is severely restricted by external factors such as seasonality, regionality, and volatility. Due to its high combustion calorific value, wide source and no pollution, hydrogen energy has extremely broad application prospects as a secondary energy storage energy.
水分解产绿氢是制备氢能源最理想的方式，整个水分解反应由析氢反应（HER）和析氧反应（OER）两个半反应组成。但高反应能垒导致了较低的HER、OER反应动力学，需要消耗更多能量来推动反应。其中Pt被证明是HER最理想催化剂，但高成本限制了其广泛应用。目前实验室研究水分解催化剂多是基于泡沫镍（NF）基底，独特的三维结构和网络状的开放通道可以带来良好的催化活性，可是极低的韧性以及装备后较大的接触阻抗大大限制了其组装在电解槽中的实际应用。目前的工业催化剂出于机械强度和循环稳定性考量多使用（NM），但其较高的过电势和较低的能量效率导致氢气制备过程中较大的能量损耗。Water splitting to produce green hydrogen is the most ideal way to produce hydrogen energy. The entire water splitting reaction consists of two half-reactions, the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). However, the high reaction energy barrier leads to lower reaction kinetics of HER and OER, requiring more energy to drive the reaction. Among them, Pt has been proved to be the most ideal catalyst for HER, but its high cost limits its wide application. At present, laboratory research on water splitting catalysts is mostly based on nickel foam (NF) substrates. The unique three-dimensional structure and network-like open channels can bring good catalytic activity, but the extremely low toughness and large contact resistance after equipment are greatly limited. The practical application of its assembly in the electrolyzer. The current industrial catalysts are mostly used (NM) due to the consideration of mechanical strength and cycle stability, but its high overpotential and low energy efficiency lead to large energy loss in the hydrogen production process.
而且采用少量掺杂Pt的方式，既可以控制住成本，也能大大提高电极性能。但Pt往往需要使用粘结剂（如Nafion）与基底结合，会导致催化剂活性位点的损失，影响电极的催化活性和催化反应速率。Moreover, the method of doping a small amount of Pt can not only control the cost, but also greatly improve the performance of the electrode. However, Pt often needs to use a binder (such as Nafion) to combine with the substrate, which will lead to the loss of catalyst active sites and affect the catalytic activity and catalytic reaction rate of the electrode.
发明内容Contents of the invention
因此，本发明要解决的技术问题在于克服现有技术中的Pt掺杂催化剂电极中的Pt通过粘结剂与基底结合，容易导致催化剂活性位点的损失，影响电极的催化活性和催化反应速率等缺陷，从而提供一种铂掺杂的催化剂电极及其制备方法和应用。Therefore, the technical problem to be solved in the present invention is to overcome the Pt in the Pt-doped catalyst electrode in the prior art combined with the substrate through the binder, which easily leads to the loss of the active site of the catalyst and affects the catalytic activity and catalytic reaction rate of the electrode. and other defects, thereby providing a platinum-doped catalyst electrode and its preparation method and application.
本发明所采取的技术方案具体如下：The technical scheme that the present invention takes is specifically as follows:
本发明提供了一种铂掺杂催化剂电极，所述催化剂电极以镍网为基体，基体上负载Ni(OH)2纳米线/片复合物作为载体，载体上掺杂不高于0.06 mg/cm2的Pt。The invention provides a platinum-doped catalyst electrode. The catalyst electrode uses a nickel mesh as a substrate, Ni(OH)2 nanowire/sheet composite is loaded on the substrate as a carrier, and the doping on the carrier is not higher than 0.06 mg/cm2 Pt.
优选的，所述Pt为纳米颗粒；Preferably, the Pt is nanoparticles;
和/或，所述Pt的掺杂量为0.04-0.06 mg/cm2。And/or, the doping amount of Pt is 0.04-0.06 mg/cm2 .
本发明还提供一种上述所述的铂掺杂催化剂电极的制备方法，包括以下步骤：The present invention also provides a method for preparing the above-mentioned platinum-doped catalyst electrode, comprising the following steps:
1）将NiCl2、尿素和水混合，得到混合溶液；1) Mix NiCl2 , urea and water to obtain a mixed solution;
2）将镍网浸入步骤1）中的混合溶液中，进行水热反应，冷却，洗涤、干燥，得到所述载体；2) Dip the nickel mesh into the mixed solution in step 1), perform hydrothermal reaction, cool, wash, and dry to obtain the carrier;
3）通过电化学沉积在骤2）中的载体表面沉积Pt，得到所述铂掺杂催化剂电极（Pt-Ni(OH)2@NM）。3) Deposit Pt on the surface of the support in step 2) by electrochemical deposition to obtain the platinum-doped catalyst electrode (Pt-Ni(OH)2 @NM).
优选的，步骤1）中NiCl2与尿素的摩尔比为1：（3-5）；Preferably, the molar ratio of NiCl2 to urea in step1 ) is 1: (3-5);
和/或，所述NiCl2与水的用量比为1：（20-30），单位为mol/L。And/or, the ratio of NiCl2 to water is 1:(20-30), and the unit is mol/L.
可选的，步骤1）各组分只要混合均匀即可，例如可经过磁力搅拌20min获得均匀的混合溶液，混合溶液为透明的绿色混合溶液。Optionally, the components in step 1) only need to be mixed uniformly, for example, a uniform mixed solution can be obtained after 20 minutes of magnetic stirring, and the mixed solution is a transparent green mixed solution.
优选的，步骤2）中所述水热反应的反应温度为110-130℃，反应时间为5-6 h；水热反应在聚四氟乙烯反应釜内衬中进行，然后自然冷却至室温；所述镍网的顶面被聚四氟乙烯胶带覆盖，使得产物在镍网的另一面沉积。Preferably, the reaction temperature of the hydrothermal reaction in step 2) is 110-130°C, and the reaction time is 5-6 h; the hydrothermal reaction is carried out in a polytetrafluoroethylene reactor lining, and then naturally cooled to room temperature; The top surface of the nickel mesh was covered with Teflon tape, allowing the product to be deposited on the other side of the nickel mesh.
优选的，步骤3）中电化学沉积的具体操作为：将步骤2）中的载体作为工作电极，氧化汞电极作为参比电极，碳棒作为对电极，组装成三电极系统置于碱性含Pt+4的电解液中进行电化学沉积。Preferably, the specific operation of electrochemical deposition in step 3) is as follows: the carrier in step 2) is used as the working electrode, the mercury oxide electrode is used as the reference electrode, and the carbon rod is used as the counter electrode, and a three-electrode system is assembled into an alkaline containing Electrochemical deposition was carried out in the electrolyte of Pt+4 .
优选的，步骤3）中所述碱性含Pt+4的电解液为1-1.2 M KOH水溶液中包含有浓度为15-20 μM的H2PtCl6；Preferably, the alkaline Pt+4 -containing electrolyte in step 3) is 1-1.2 M KOH aqueous solution containing H2 PtCl6 at a concentration of 15-20 μM;
和/或，所述电化学沉积选用循环伏安法，扫描速率为40-60 mV/s，电压范围-0.5-0 V，循环周期为40-50周。And/or, the electrochemical deposition adopts cyclic voltammetry, the scan rate is 40-60 mV/s, the voltage range is -0.5-0 V, and the cycle period is 40-50 cycles.
优选的，步骤2）中所述洗涤的溶剂依次为水、乙醇；先用去离子水清洗再用乙醇清洗；Preferably, the washing solvents in step 2) are water and ethanol in sequence; first wash with deionized water and then wash with ethanol;
和/或，洗涤次数分别为3-5次；And/or, the times of washing are 3-5 times respectively;
和/或，所述干燥温度为60-80℃，干燥时间为12-24 h；可选但不限于真空干燥。And/or, the drying temperature is 60-80° C., and the drying time is 12-24 h; optional but not limited to vacuum drying.
优选的，步骤2）中所述镍网预先经过清洗处理；Preferably, the nickel mesh described in step 2) is pre-cleaned;
和/或，所述镍网依次经过丙酮、乙醇、去离子水、盐酸水溶液和去离子水清洗；And/or, the nickel mesh is washed successively through acetone, ethanol, deionized water, hydrochloric acid aqueous solution and deionized water;
和/或，盐酸水溶液的浓度为2-3 M HCl；And/or, the concentration of aqueous hydrochloric acid is 2-3 M HCl;
和/或，清洗为超声清洗，每种溶剂清洗时间为10-20 min。And/or, the cleaning is ultrasonic cleaning, and the cleaning time of each solvent is 10-20 min.
可选的，镍网清洗处理后干燥，典型非限定性的，在60℃真空干燥箱中干燥12 h。Optionally, the nickel mesh is cleaned and dried, typically but not limited, in a vacuum oven at 60°C for 12 h.
本发明还提供一种上述所述的铂掺杂催化剂电极或由上述所述方法制备的铂掺杂催化剂电极在电解水中的应用。The present invention also provides an application of the above-mentioned platinum-doped catalyst electrode or the platinum-doped catalyst electrode prepared by the above-mentioned method in electrolyzing water.
本发明技术方案，具有如下优点：The technical solution of the present invention has the following advantages:
（1）本发明提供的铂掺杂催化剂电极，所述催化剂电极以镍网为基体，基体上负载Ni(OH)2纳米线/片复合物作为载体，载体上掺杂不高于0.06 mg/cm2的Pt。本发明的镍网基体有助于构建Ni(OH)2纳米线/片复合结构，Ni(OH)2纳米线/片二维材料的特性大大提高了材料整体的表面积，并有利于Pt的负载和锚定，Pt与基底特殊的结合方式对活性位点的提高以及循环寿命的维持有重要作用；本发明通过Pt掺杂和Ni(OH)2结构的协同效应共同调节了电极的电荷动力学、电化学活性面积和活性位点的本征活性，从而优化催化剂整体的HER/OER催化活性和催化反应速率，降低反应能耗。本发明的催化剂制备的电极电解水性能以及循环寿命优势强，有助于在实际工况中应用。(1) The platinum-doped catalyst electrode provided by the present invention, the catalyst electrode is based on a nickel mesh, and the Ni(OH)2 nanowire/sheet composite is loaded on the substrate as a carrier, and the doping on the carrier is not higher than 0.06 mg/ cm2 of Pt. The nickel mesh matrix of the present invention helps to construct Ni(OH)2nanowire /sheet composite structure, and the characteristics of Ni(OH)2nanowire /sheet two-dimensional material greatly improve the overall surface area of the material and are conducive to the loading of Pt And anchoring, the special combination of Pt and substrate plays an important role in the improvement of active sites and the maintenance of cycle life; the present invention jointly adjusts the charge dynamics of the electrode through the synergistic effect of Pt doping and Ni(OH)2 structure , the electrochemical active area and the intrinsic activity of the active site, so as to optimize the overall HER/OER catalytic activity and catalytic reaction rate of the catalyst, and reduce the energy consumption of the reaction. The electrode prepared by the catalyst of the present invention has strong advantages in water electrolysis performance and cycle life, and is helpful for application in actual working conditions.
（2）本发明提供的铂掺杂催化剂电极，掺杂的Pt为纳米颗粒，Pt的掺杂量为0.04-0.06 mg/cm2，进一步限定了Pt的掺杂情况，在降低成本的同时进一步提高了贵金属的利用率，大大提升催化剂电极的电化学活性面积，降低反应能耗。(2) In the platinum-doped catalyst electrode provided by the present invention, the doped Pt is nanoparticles, and the doping amount of Pt is 0.04-0.06 mg/cm2 , which further limits the doping of Pt, and further reduces the cost while reducing the cost. The utilization rate of the precious metal is improved, the electrochemically active area of the catalyst electrode is greatly increased, and the energy consumption of the reaction is reduced.
（3）本发明提供的铂掺杂催化剂电极的制备方法，包括以下步骤：1）将NiCl2、尿素和水混合，得到混合溶液；2）将镍网浸入步骤1）中的混合溶液中，进行水热反应，冷却，洗涤、干燥，得到所述载体；3）通过电化学沉积在骤2）中的载体表面沉积Pt，得到铂掺杂催化剂电极。本发明通过水热反应在基底上形成Ni(OH)2纳米线/纳米片结构，纳米线是在水热反应过程中由纳米片卷积形成。同时在Ni(OH)2纳米线/片复合结构上利用电化学沉积Pt，更有利于Pt的有效负载和锚定，提高活性位点，维持循环寿命，整体优化催化剂电极的活性和催化反应速率。(3) The preparation method of the platinum-doped catalyst electrode provided by the present invention comprises the following steps: 1) mixing NiCl2 , urea and water to obtain a mixed solution; 2) immersing the nickel mesh in the mixed solution in step 1), performing a hydrothermal reaction, cooling, washing and drying to obtain the carrier; 3) depositing Pt on the surface of the carrier in step 2) by electrochemical deposition to obtain a platinum-doped catalyst electrode. The invention forms a Ni(OH)2 nanowire/nanosheet structure on a substrate through a hydrothermal reaction, and the nanowire is formed by convolution of the nanosheet during the hydrothermal reaction. At the same time, the use of electrochemical deposition of Pt on the Ni(OH)2 nanowire/sheet composite structure is more conducive to the effective loading and anchoring of Pt, improving the active sites, maintaining the cycle life, and optimizing the activity and catalytic reaction rate of the catalyst electrode as a whole. .
附图说明Description of drawings
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings that need to be used in the description of the specific embodiments or prior art. Obviously, the accompanying drawings in the following description The drawings show some implementations of the present invention, and those skilled in the art can also obtain other drawings based on these drawings without creative work.
图1 是本发明实施例1提供的铂掺杂催化剂电极的制备流程图；Fig. 1 is the preparation flow diagram of the platinum-doped catalyst electrode provided by Example 1 of the present invention;
图2 是本发明实施例1（b）、对比例1（a）、对比例2（b）、对比例3（a）、对比例4（b）、对比例5（a）以及对应的基底NM（b）、NF（a）的XRD谱图；Figure 2 shows Example 1 (b), Comparative Example 1 (a), Comparative Example 2 (b), Comparative Example 3 (a), Comparative Example 4 (b), Comparative Example 5 (a) and the corresponding substrates of the present invention XRD spectra of NM(b) and NF(a);
图3 是本发明实施例1（d）、对比例2（b）、对比例4（c）以及所用基底NM（a）的SEM照片；Fig. 3 is the SEM photo of Example 1 (d) of the present invention, Comparative Example 2 (b), Comparative Example 4 (c) and the substrate NM (a) used;
图4 是本发明对比例1（d）、对比例3（b）、与对比例5（c）以及使用的基底NF（a）的SEM照片；Figure 4 is the SEM photos of Comparative Example 1 (d), Comparative Example 3 (b), Comparative Example 5 (c) and the substrate NF (a) used in the present invention;
图5 是本发明实施例1和对比例1的SEM和TEM照片，其中，a为实施例1中Pt-Ni(OH)2@NM的SEM照片，b、c为其TEM照片；d为对比例1中Pt-Ni(OH)2@NF的SEM照片，e、f为其TEM照片；Fig. 5 is the SEM and TEM photos of Example 1 and Comparative Example 1 of the present invention, wherein, a is the SEM photo of Pt-Ni(OH)2 @NM in Example 1, b and c are its TEM photos; d is the pair SEM photos of Pt-Ni(OH)2 @NF in
图6 是本发明实施例1的（a）SEM照片；（b）TEM照片，插图是对应区域的SAED衍射花样和颗粒直径统计直方图；（c，d）HRTEM照片；（e）选定区域的傅里叶/反傅里叶变换图和晶格条纹测量截图；（f）TEM能谱图；Figure 6 is (a) SEM photo of Example 1 of the present invention; (b) TEM photo, the illustration is the SAED diffraction pattern and particle diameter statistical histogram of the corresponding area; (c, d) HRTEM photo; (e) selected area Fourier/inverse Fourier transform map and screenshot of lattice fringe measurement; (f) TEM energy spectrum;
图7 是本发明实施例1-3和对比例1-6的催化剂电极以及所用基底的HER（a）极化曲线，（b）Tafel斜率曲线；Fig. 7 is the HER (a) polarization curve and (b) Tafel slope curve of the catalyst electrodes and substrates used in Examples 1-3 and Comparative Examples 1-6 of the present invention;
图8 是本发明实施例1-3和对比例1-5、7的催化剂电极以及所用基底的OER（a）极化曲线，（b）Tafel斜率曲线；Fig. 8 is the OER (a) polarization curve and (b) Tafel slope curve of the catalyst electrode and substrate used in Examples 1-3 of the present invention and Comparative Examples 1-5, 7;
图9 是本发明实施例1的全水解三电极系统化曲线（a）、实施例1组合、对比例6和对比例7组合组装的全水解双电级系统极化曲线（b）；Figure 9 is the full hydrolysis three-electrode systematization curve (a) of Example 1 of the present invention, the polarization curve (b) of the full hydrolysis double-electrode system assembled by the combination of Example 1, Comparative Example 6 and Comparative Example 7;
图10 是本发明实施例1 Pt-Ni(OH)2@NM的（a）HER，（b）OER和（c）全水解双电级系统的循环寿命曲线，插图为恒电位测试曲线；Figure 10 is the cycle life curve of (a) HER, (b) OER and (c) fully hydrolyzed double-electrode system of Pt-Ni(OH)2 @NM in Example 1 of the present invention, and the inset is the potentiostatic test curve;
图11是本发明实施例1 Pt-Ni(OH)2@NM和基底NM，对比例1 Pt-Ni(OH)2@NF以及对比例6、7的组合（Pt/C@NM || RuO2@NM）组装到碱性水电解槽的（a）电解槽结构示意图，（b）极化曲线，（c）400 mA/cm2和1000 mA/cm2的电压对比图，（d）阻抗图；实施例1的催化剂电极和基底的成本、电压消耗对比图（e）；实施例1和对比例1的电压-时间曲线（f）。Figure 11 is the combination of Example 1 Pt-Ni(OH)2 @NM and substrate NM of the present invention, Comparative Example 1 Pt-Ni(OH)2 @NF and Comparative Examples 6 and 7 (Pt/C@NM || RuO2 @NM) (a) Schematic diagram of electrolyzer structure assembled into alkaline water electrolyzer, (b) polarization curve, (c) voltage comparison diagram of 400 mA/cm2 and 1000 mA/cm2 , (d) impedance Figure; Cost and Voltage Consumption Comparison Chart (e) of Catalyst Electrode and Substrate in Example 1; Voltage-Time Curve (f) of Example 1 and Comparative Example 1.
具体实施方式Detailed ways
提供下述实施例是为了更好地进一步理解本发明，并不局限于所述最佳实施方式，不对本发明的内容和保护范围构成限制，任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品，均落在本发明的保护范围之内。The following examples are provided in order to further understand the present invention better, are not limited to the best implementation mode, and do not limit the content and protection scope of the present invention, anyone under the inspiration of the present invention or use the present invention Any product identical or similar to the present invention obtained by combining features of other prior art falls within the protection scope of the present invention.
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。If no specific experimental steps or conditions are indicated in the examples, it can be carried out according to the operation or conditions of the conventional experimental steps described in the literature in this field. The reagents or instruments used, whose manufacturers are not indicated, are all commercially available conventional reagent products.
实施例1Example 1
本实施例提供的铂掺杂催化剂电极，以镍网（NM，河北超创金属网业，100目镍网，3×3 cm2）为基体，基体上负载Ni(OH)2纳米线/片复合物作为载体，载体上掺杂0.06 mg/cm2的纳米Pt。The platinum-doped catalyst electrode provided in this example uses a nickel mesh (NM, Hebei Chaochuang Metal Mesh Industry, 100-mesh nickel mesh, 3×3 cm2 ) as the substrate, and Ni(OH)2 nanowires/sheet are loaded on the substrate The composite is used as a carrier, and the carrier is doped with 0.06 mg/cm2 nanometer Pt.
本实施例提供的铂掺杂催化剂电极的制备方法，工艺流程如图1所示，包括以下步骤：The preparation method of the platinum-doped catalyst electrode provided in this example, the process flow is shown in Figure 1, including the following steps:
1）干净NM的制备方法：1) Preparation method of clean NM:
将裁剪好的镍网NM分别用丙酮、乙醇、去离子水、3 M HCl和去离子水，依次超声清洗，每种试剂清洗10 min，然后在60 ℃真空干燥箱中干燥12 h，得到干净NM。The cut nickel mesh NM was cleaned with acetone, ethanol, deionized water, 3 M HCl and deionized water, respectively, and ultrasonically cleaned for 10 min for each reagent, and then dried in a vacuum oven at 60 °C for 12 h to obtain a clean NM.
2）基于NM基底的Ni(OH)2纳米线/片复合结构（Ni(OH)2@NM）的制备：2) Preparation of Ni(OH)2 nanowire/sheet composite structure (Ni(OH)2 @NM) based on NM substrate:
利用一步典型的水热反应，将4 mmol NiCl2和16 mmol尿素溶解在100 mL去离子水中，磁力搅拌20 min以获得透明的绿色溶液。接着，将混合溶液倒入聚四氟乙烯反应釜内衬，并取一片干净的NM浸入其中（NM的顶面被聚四氟乙烯胶带覆盖，使得产物在镍网的另一面沉积）。随后，将反应釜在120 ℃下保持6 h，自然冷却到室温。最后，取出NM先用去离子水冲洗3次，再用乙醇冲洗3次，在80 ℃真空干燥箱中干燥12 h，得到Ni(OH)2@NM。Using one-step typical hydrothermal reaction,4 mmol NiCl2 and 16 mmol urea were dissolved in 100 mL deionized water and magnetically stirred for 20 min to obtain a transparent green solution. Next, the mixed solution was poured into the Teflon reactor liner, and a piece of clean NM was dipped into it (the top surface of the NM was covered with Teflon tape so that the product was deposited on the other side of the nickel mesh). Subsequently, the reactor was kept at 120 °C for 6 h and cooled to room temperature naturally. Finally, the NM was taken out and rinsed three times with deionized water, then three times with ethanol, and dried in a vacuum oven at 80 ℃ for 12 h to obtain Ni(OH)2 @NM.
3）基于NM基底的Pt掺杂Ni(OH)2催化剂电极（Pt-Ni(OH)2@NM）的制备：3) Preparation of Pt-doped Ni(OH)2 catalyst electrode (Pt-Ni(OH)2 @NM) based on NM substrate:
目标样品Pt-Ni(OH)2@NM是通过电沉积法制备的。Ni(OH)2@NM被组装成三电极系统，其中Ni(OH)2@NM作为工作电极，氧化汞电极作为参比电极，碳棒作为对电极。对应的电化学过程是在包含20 μM H2PtCl6的1 M KOH电解液中，通过循环CV阴极极化过程实现的，扫描速度为50 mV/s， -0.5-0 V相对RHE循环50周，得到Pt-Ni(OH)2@NM，经电感耦合等离子体发射光谱仪（ICP-OES）测试，Pt掺杂量为0.06 mg/cm2。The target sample Pt-Ni(OH)2 @NM was prepared by electrodeposition. Ni(OH)2 @NM was assembled into a three-electrode system, in which Ni(OH)2 @NM was used as the working electrode, the mercury oxide electrode was used as the reference electrode, and the carbon rod was used as the counter electrode. The corresponding electrochemical process was achieved by a cyclic CV cathodic polarization process in a1 M KOH electrolyte containing 20 μMH2PtCl6 at a scan rate of 50 mV/s at -0.5-0 V versus RHE for 50 cycles , to obtain Pt-Ni(OH)2 @NM, which was tested by inductively coupled plasma optical emission spectrometer (ICP-OES), and the Pt doping amount was 0.06 mg/cm2 .
实施例2Example 2
本实施例提供的铂掺杂催化剂电极，以NM为基体，基体上负载Ni(OH)2纳米线/片复合物作为载体，载体上掺杂0.05 mg/cm2的纳米Pt。The platinum-doped catalyst electrode provided in this example uses NM as a substrate, Ni(OH)2 nanowire/sheet composite is supported on the substrate as a carrier, and the carrier is doped with 0.05 mg/cm2 nano-Pt.
本实施例提供的铂掺杂催化剂电极的制备方法，工艺流程如图1所示，包括以下步骤：The preparation method of the platinum-doped catalyst electrode provided in this example, the process flow is shown in Figure 1, including the following steps:
1）干净NM的制备方法：1) Preparation method of clean NM:
将裁剪好的镍网NM分别用丙酮、乙醇、去离子水、2 M HCl和去离子水，依次超声清洗，每种试剂清洗15 min，然后在60 ℃真空干燥箱中干燥12 h，得到干净NM。The cut nickel mesh NM was cleaned with acetone, ethanol, deionized water, 2 M HCl and deionized water, respectively, and ultrasonically cleaned for 15 min for each reagent, and then dried in a vacuum oven at 60 °C for 12 h to obtain a clean NM.
2）基于NM基底的Ni(OH)2纳米线/片复合结构（Ni(OH)2@NM）的制备：2) Preparation of Ni(OH)2 nanowire/sheet composite structure (Ni(OH)2 @NM) based on NM substrate:
利用一步典型的水热反应，将4 mmol NiCl2和20 mmol尿素溶解在120 mL去离子水中，磁力搅拌20 min以获得透明的绿色溶液。接着，将混合溶液倒入聚四氟乙烯反应釜内衬，并取一片干净的NM浸入其中（NM的顶面被聚四氟乙烯胶带覆盖，使得产物在镍网的另一面沉积）。随后，将反应釜在130 ℃下保持5 h，自然冷却到室温。最后，取出NM先用去离子水冲洗5次，再用乙醇冲洗5次，在60 ℃真空干燥箱中干燥24 h，得到Ni(OH)2@NM。Using one-step typical hydrothermal reaction, 4 mmol NiCl2 and20 mmol urea were dissolved in 120 mL deionized water and magnetically stirred for 20 min to obtain a transparent green solution. Next, the mixed solution was poured into the Teflon reactor liner, and a piece of clean NM was dipped into it (the top surface of the NM was covered with Teflon tape so that the product was deposited on the other side of the nickel mesh). Subsequently, the reactor was kept at 130 °C for 5 h and cooled to room temperature naturally. Finally, the NM was taken out and washed 5 times with deionized water, then with
3）基于NM基底的Pt掺杂Ni(OH)2催化剂电极的制备：3) Preparation of Pt-doped Ni(OH)2 catalyst electrode based on NM substrate:
目标样品Pt-Ni(OH)2@NM是通过电沉积法制备的。Ni(OH)2@NM被组装成三电极系统，其中Ni(OH)2@NM作为工作电极，氧化汞电极作为参比电极，碳棒作为对电极。对应的电化学过程是在包含17 μM H2PtCl6的 1.2 M KOH电解液中，通过循环CV阴极极化过程实现的，扫描速度为60 mV/s， -0.5-0 V相对RHE循环50周，得到所述催化剂电极。经ICP-OES测试，Pt掺杂量0.05mg/cm2。The target sample Pt-Ni(OH)2 @NM was prepared by electrodeposition. Ni(OH)2 @NM was assembled into a three-electrode system, in which Ni(OH)2 @NM was used as the working electrode, the mercury oxide electrode was used as the reference electrode, and the carbon rod was used as the counter electrode. The corresponding electrochemical process was achieved by a cyclic CV cathodic polarization process in a 1.2 M KOH electrolyte containing17 μMH2PtCl6 at a scan rate of 60 mV/s at -0.5-0 V versus RHE for 50 cycles , to obtain the catalyst electrode. As tested by ICP-OES, the Pt doping amount is 0.05 mg/cm2 .
实施例3Example 3
本实施例提供的铂掺杂催化剂电极，以NM为基体，基体上负载Ni(OH)2纳米线/片复合物作为载体，载体上掺杂0.04 mg/cm2的纳米Pt。The platinum-doped catalyst electrode provided in this example uses NM as a substrate, Ni(OH)2 nanowire/sheet composite is loaded on the substrate as a carrier, and the carrier is doped with 0.04 mg/cm2 nano-Pt.
本实施例提供的铂掺杂催化剂电极的制备方法，工艺流程如图1所示，包括以下步骤：The preparation method of the platinum-doped catalyst electrode provided in this example, the process flow is shown in Figure 1, including the following steps:
1）干净NM的制备方法：1) Preparation method of clean NM:
将裁剪好的镍网NM分别用丙酮、乙醇、去离子水、3 M HCl和去离子水，依次超声清洗，每种试剂清洗13 min，然后在60℃真空干燥箱中干燥12 h，得到干净NM。The cut nickel mesh NM was ultrasonically cleaned with acetone, ethanol, deionized water, 3 M HCl and deionized water respectively, each reagent was cleaned for 13 min, and then dried in a vacuum oven at 60 °C for 12 h to obtain a clean NM.
2）基于NM基底的Ni(OH)2纳米线/片复合结构（Ni(OH)2@NM）的制备：2) Preparation of Ni(OH)2 nanowire/sheet composite structure (Ni(OH)2 @NM) based on NM substrate:
利用一步典型的水热反应，将4 mmol NiCl2和12 mmol尿素溶解在80 mL去离子水中，磁力搅拌20 min以获得透明的绿色溶液。接着，将混合溶液倒入聚四氟乙烯反应釜内衬，并取一片干净的NM浸入其中（NM的顶面被聚四氟乙烯胶带覆盖，使得产物在镍网的另一面沉积）。随后，将反应釜在110 ℃下保持6 h，自然冷却到室温。最后，取出NM先用去离子水冲洗4次，再用乙醇冲洗4次，在80 ℃真空干燥箱中干燥12 h，得到Ni(OH)2@NM。Using one-step typical hydrothermal reaction,4 mmol NiCl2 and 12 mmol urea were dissolved in 80 mL deionized water and magnetically stirred for 20 min to obtain a transparent green solution. Next, the mixed solution was poured into the Teflon reactor liner, and a piece of clean NM was dipped into it (the top surface of the NM was covered with Teflon tape so that the product was deposited on the other side of the nickel mesh). Subsequently, the reactor was kept at 110 °C for 6 h and cooled to room temperature naturally. Finally, the NM was taken out and rinsed with deionized water for 4 times, and then with ethanol for 4 times, and dried in a vacuum oven at 80 ℃ for 12 h to obtain Ni(OH)2 @NM.
3）基于NM基底的Pt掺杂Ni(OH)2催化剂电极的制备：3) Preparation of Pt-doped Ni(OH)2 catalyst electrode based on NM substrate:
目标样品Pt-Ni(OH)2@NM是通过电沉积法制备的。Ni(OH)2@NM被组装成三电极系统，其中Ni(OH)2@NM作为工作电极，氧化汞电极作为参比电极，碳棒作为对电极。对应的电化学过程是在包含15 μM H2PtCl6的 1.1 M KOH电解液中，通过循环CV阴极极化过程实现的，扫描速度为40 mV/s，-0.5-0 V相对RHE循环40周，得到所述催化剂电极，经ICP-OES测试，Pt掺杂量0.04 mg/cm2。The target sample Pt-Ni(OH)2 @NM was prepared by electrodeposition. Ni(OH)2 @NM was assembled into a three-electrode system, in which Ni(OH)2 @NM was used as the working electrode, the mercury oxide electrode was used as the reference electrode, and the carbon rod was used as the counter electrode. The corresponding electrochemical process was achieved by a cyclic CV cathodic polarization process in a 1.1 M KOH electrolyte containing15 μMH2PtCl6 at a scan rate of 40 mV/s at -0.5-0 V vs. RHE for 40 cycles , to obtain the catalyst electrode, tested by ICP-OES, the Pt doping amount is 0.04 mg/cm2 .
对比例1Comparative example 1
本对比例提供的催化剂电极，以泡沫镍（NF，赛博电化学材料网，1.5 mm厚，孔径0.2-0.6 mm，孔隙率97.2%）为基体，基体上负载Ni(OH)2纳米线/片复合物作为载体，载体上掺杂0.11 mg/cm2的纳米Pt。The catalyst electrode provided in this comparative example is based on nickel foam (NF, Cyber Electrochemical Material Network, 1.5 mm thick, pore diameter 0.2-0.6 mm, porosity 97.2%), and Ni(OH)2 nanowires/ The flake composite is used as a carrier, and the carrier is doped with 0.11 mg/cm2 nanometer Pt.
本对比例提供催化剂电极的制备方法，包括以下步骤：This comparative example provides the preparation method of catalyst electrode, comprises the following steps:
将实施例1中的NM替换为泡沫镍（NF），其余步骤不变，得到以NF为基底的催化剂Pt-Ni(OH)2@NF，经ICP-OES测试，Pt掺杂量0.11 mg/cm2。The NM in Example 1 was replaced by nickel foam (NF), and the rest of the steps remained unchanged to obtain the NF-based catalyst Pt-Ni(OH)2 @NF, which was tested by ICP-OES, and the Pt doping amount was 0.11 mg/ cm2 .
对比例2Comparative example 2
本对比例提供的催化剂电极，以NM为基体，基体上负载Ni(OH)2纳米线/片复合物。The catalyst electrode provided in this comparative example uses NM as the substrate, and the Ni(OH)2 nanowire/sheet composite is supported on the substrate.
本对比例提供催化剂电极的制备方法，包括实施例1的步骤1）和步骤2），得到的载体即为本对比例的催化剂Ni(OH)2@NM。This comparative example provides a method for preparing a catalyst electrode, including step 1) and step 2) of Example 1, and the obtained carrier is the catalyst Ni(OH)2 @NM of this comparative example.
对比例3Comparative example 3
本对比例提供的催化剂电极，以NF为基体，基体上负载Ni(OH)2纳米线/片复合物。The catalyst electrode provided in this comparative example uses NF as the matrix, and the Ni(OH)2 nanowire/sheet composite is loaded on the matrix.
本对比例提供催化剂电极的制备方法，包括实施例2的步骤1）和步骤2），得到的载体即为本对比例的催化剂Ni(OH)2@NF。This comparative example provides a method for preparing a catalyst electrode, including step 1) and step 2) of Example 2, and the obtained carrier is the catalyst Ni(OH)2 @NF of this comparative example.
对比例4Comparative example 4
本对比例提供的催化剂电极，以NM为基体，基体上负载Pt。The catalyst electrode provided in this comparative example uses NM as a substrate, and Pt is loaded on the substrate.
本对比例提供催化剂电极的制备方法，包括以下步骤：This comparative example provides the preparation method of catalyst electrode, comprises the following steps:
将NM作为工作电极，氧化汞电极作为参比电极，碳棒作为对电极。对应的电化学过程是在包含20 μM H2PtCl6的 1 M KOH电解液中，通过循环CV阴极极化过程实现的，扫描速度为50 mV/s，-0.5-0 V相对RHE循环50周，得到催化剂Pt@NM。经ICP-OES测定，Pt掺杂量0.03 mg/cm2。The NM was used as the working electrode, the mercury oxide electrode was used as the reference electrode, and the carbon rod was used as the counter electrode. The corresponding electrochemical process was achieved by a cyclic CV cathodic polarization process in a1 M KOH electrolyte containing 20 μMH2PtCl6 at a scan rate of 50 mV/s, −0.5–0 V versus RHE for 50 cycles , to obtain the catalyst Pt@NM. As determined by ICP-OES, the Pt doping amount is 0.03 mg/cm2 .
对比例5Comparative example 5
本对比例提供的催化剂电极，以NF为基体，基体上负载Pt。The catalyst electrode provided in this comparative example uses NF as a substrate, and Pt is loaded on the substrate.
本对比例提供催化剂电极的制备方法，包括以下步骤：This comparative example provides the preparation method of catalyst electrode, comprises the following steps:
将对比例1中的NM替换为泡沫镍（NF），其余步骤不变，得到铂掺杂催化剂Pt@NF。经ICP-OES测定，Pt掺杂量0.07 mg/cm2。The NM in Comparative Example 1 was replaced by nickel foam (NF), and the rest of the steps remained unchanged to obtain the platinum-doped catalyst Pt@NF. As determined by ICP-OES, the Pt doping amount is 0.07 mg/cm2 .
对比例6Comparative example 6
本对比例提供的催化剂电极，以NM为基体，基体上负载商业20% Pt/C（品牌：Macklin，规格：Pt 20%）。The catalyst electrode provided in this comparative example uses NM as the substrate, and the substrate is loaded with commercial 20% Pt/C (brand: Macklin, specification:
本对比例提供催化剂电极的制备方法，包括以下步骤：This comparative example provides the preparation method of catalyst electrode, comprises the following steps:
将10mg购买的商业20% Pt/C分散在330 μL水/乙醇/5%Nafion（伊诺凯试剂Innochem，Nafion117）溶剂(V/V/V=150:150:30)中，超声20 min。将制备的催化剂溶液滴在NM基底上，并自然晾干，得到Pt/C@NM。经ICP-OES测试，Pt掺杂量0.5 mg/cm2。Disperse 10 mg of purchased commercial 20% Pt/C in 330 μL water/ethanol/5% Nafion (Innochem, Nafion117) solvent (V/V/V=150:150:30) and sonicate for 20 min. The prepared catalyst solution was dropped on the NM substrate and allowed to dry naturally to obtain Pt/C@NM. According to the ICP-OES test, the Pt doping amount is 0.5 mg/cm2 .
对比例7Comparative example 7
本对比例提供的催化剂电极，以NM为基体，基体上负载商业RuO2。The catalyst electrode provided in this comparative example uses NM as a substrate, and commercial RuO2 is loaded on the substrate.
本对比例提供催化剂电极的制备方法，包括以下步骤：This comparative example provides the preparation method of catalyst electrode, comprises the following steps:
将10mg购买的商业RuO2（品牌：Macklin，规格：99.9%）分散在330 μL水/乙醇/5%Nafion溶剂(V/V/V=150:150:30)中，超声20 nim。将制备的催化剂溶液滴在NM基底上，并自然晾干，得到RuO2@NM。经ICP-OES测试，Ru掺杂量0.8 mg/cm2。Disperse 10 mg of purchased commercial RuO2 (brand: Macklin, specification: 99.9%) in 330 μL of water/ethanol/5% Nafion solvent (V/V/V=150:150:30), and sonicate at 20 nm. The prepared catalyst solution was dropped on the NM substrate and dried naturally to obtain RuO2 @NM. According to the ICP-OES test, the Ru doping amount is 0.8 mg/cm2 .
对实施例和对比例进行了以下测试：Carried out following test to embodiment and comparative example:
1. 结构测试1. Structural testing
对实施例1-3和对比例1-7制备得到的催化剂电极以及基底进行ICP-OES元素含量测定以及XRD、SEM、TEM、SAED衍射、颗粒直径统计、HRTEM、傅里叶/反傅里叶变换、TEM能谱等结构测试。ICP-OES element content determination and XRD, SEM, TEM, SAED diffraction, particle diameter statistics, HRTEM, Fourier/inverse Fourier were carried out on the catalyst electrodes and substrates prepared in Examples 1-3 and Comparative Examples 1-7 Transformation, TEM energy spectrum and other structural tests.
测试结果如下所示：The test results are as follows:
表1是通过ICP-OES测定本发明实施例1-3和对比例1-7的样品元素含量。因为使用的Ni基底，所以Ni质量主要为基底质量。Table 1 is the sample element contents of Examples 1-3 and Comparative Examples 1-7 of the present invention determined by ICP-OES. Because of the Ni substrate used, the Ni mass is mainly the substrate mass.
表1Table 1
图2是本发明实施例1 Pt-Ni(OH)2@NM（b）、对比例1 Pt-Ni(OH)2@NF（a）、对比例2Ni(OH)2@NM（b）、对比例3 Ni(OH)2@NF（a）、对比例4 Pt@NM（b）、对比例5 Pt@NF（a）以及对应的基底NM（b）、NF（a）的XRD谱图。Fig. 2 is Example 1 Pt-Ni(OH)2 @NM (b) of the present invention, Comparative Example 1 Pt-Ni(OH)2 @NF (a), Comparative Example 2 Ni(OH)2 @NM (b), XRD patterns of Comparative Example 3 Ni(OH)2 @NF (a), Comparative Example 4 Pt@NM (b), Comparative Example 5 Pt@NF (a) and the corresponding substrates NM (b) and NF (a) .
从图中可以看出：在Ni(OH)2生长后有对应的特征峰出现，但是因为NM和NF中Ni单质过强的屏蔽作用，导致Ni(OH)2和Pt的特征峰强度较弱，需借助其他手段辅助表征。It can be seen from the figure that after the growth of Ni(OH)2 , there are corresponding characteristic peaks, but because of the strong shielding effect of Ni in NM and NF, the characteristic peak intensities of Ni(OH)2 and Pt are weak , it is necessary to use other means to assist in the characterization.
图3是本发明实施例1 Pt-Ni(OH)2@NM（d）、对比例2 Ni(OH)2@NM（b）、对比例4 Pt@NM（c）以及所用基底NM（a）的SEM照片。Figure 3 shows Example 1 Pt-Ni(OH)2 @NM (d) of the present invention, Comparative Example 2 Ni(OH)2 @NM (b), Comparative Example 4 Pt@NM (c) and the substrate NM used (a ) SEM photographs.
从图中可以看出：水热法后，Ni(OH)2@NM可经标尺测量到大量宽度约为10nm的Ni(OH)2纳米线阵列生长在NM基底上，形貌致密且均匀；而直接沉积的Pt堆叠成直径约为30nm的颗粒；Pt-Ni(OH)2@NM的微观形貌与Ni(OH)2@NM一致，也是纳米线阵列。在Ni(OH)2纳米线表面沉积的Pt，100 nm标尺下也无法直接观测到，说明Pt颗粒细小。说明Pt颗粒越细小，分散的面积越大，贵金属利用率越高，成本越低。It can be seen from the figure that after the hydrothermal method, Ni(OH)2 @NM can be measured by a ruler, and a large number of Ni(OH)2 nanowire arrays with a width of about 10 nm grow on the NM substrate, and the morphology is dense and uniform; The directly deposited Pt stacks into particles with a diameter of about 30 nm; the microscopic morphology of Pt-Ni(OH)2 @NM is consistent with that of Ni(OH)2 @NM, which is also a nanowire array. The Pt deposited on the surface of Ni(OH)2 nanowires cannot be directly observed under the 100 nm scale, indicating that the Pt particles are small. It shows that the finer the Pt particles, the larger the dispersed area, the higher the utilization rate of the precious metal, and the lower the cost.
图4是本发明对比例1 Pt-Ni(OH)2@NF（d）、对比例3 Ni(OH)2@NF（b）、与对比例5的Pt@NF（c）以及使用的基底NF（a）的SEM照片。Figure 4 is the comparison example 1 Pt-Ni(OH)2 @NF (d) of the present invention, the comparison example 3 Ni(OH)2 @NF (b), and the Pt@NF (c) of the comparison example 5 and the substrate used SEM photograph of NF(a).
从图中可以看出，NF基底样品与NM基底样品的形貌规律类似，表现出纳米线/纳米片复合结构，但因NM基底机械强度低，复合结构有轻微坍塌。It can be seen from the figure that the morphology of the NF substrate sample is similar to that of the NM substrate sample, showing a nanowire/nanosheet composite structure, but due to the low mechanical strength of the NM substrate, the composite structure has a slight collapse.
图5是本发明实施例1 Pt-Ni(OH)2@NM（a）SEM和（b、c）TEM照片；对比例1 Pt-Ni(OH)2@NF的（d）SEM和（e、f）TEM照片。Figure 5 is the (a) SEM and (b, c) TEM photos of Pt-Ni(OH)2 @NM in Example 1 of the present invention; (d) SEM and (e) of Comparative Example 1 Pt-Ni(OH)2 @NF , f) TEM photo.
从图中可以看出，虽然在两幅SEM照片中只能看到密集的纳米线阵列，但经过TEM测试前常规的超声波处理剥离基底表面的结构后，低倍TEM照片中就可以观测到非常多的纳米片碎屑。在较高的倍数下可以看出，纳米线生长的位置都是纳米片的边缘，由纳米片卷积形成。其中，使用标尺测量，Pt-Ni(OH)2@NF的纳米线约10 nm，而Pt-Ni(OH)2@NM中的纳米线更细小，约5 nm。It can be seen from the figure that although only a dense array of nanowires can be seen in the two SEM photos, after the conventional ultrasonic treatment before the TEM test to peel off the structure of the substrate surface, a very large nanowire array can be observed in the low-magnification TEM photos. Lots of nanosheet debris. At higher magnifications, it can be seen that the nanowires grow at the edges of the nanosheets, formed by the convolution of the nanosheets. Among them, using a ruler, the nanowires of Pt-Ni(OH)2 @NF are about 10 nm, while the nanowires of Pt-Ni(OH)2 @NM are smaller, about 5 nm.
图6是本发明实施例1 Pt-Ni(OH)2@NM的（a）SEM照片；（b）TEM照片，插图是对应区域的SAED衍射花样和颗粒直径统计直方图；（c，d）HRTEM照片；（e）选定区域的傅里叶/反傅里叶变换图和晶格条纹测量截图；（f）TEM能谱图。Figure 6 is the (a) SEM photo of Pt-Ni(OH)2 @NM in Example 1 of the present invention; (b) TEM photo, the inset is the SAED diffraction pattern and particle diameter statistical histogram of the corresponding area; (c, d) HRTEM image; (e) Fourier/inverse Fourier transform map of the selected area and screenshot of lattice fringe measurement; (f) TEM energy spectrum.
从图中可以看出，一些直径约3.14 nm的Pt纳米颗粒牢固地锚定在Ni(OH)2纳米线/片复合结构中。SAED衍射图与Ni(OH)2的（100），（102）和（110）晶面和Pt（111）晶面对应，这与XRD结果一致。HRTEM图看到深色的Pt纳米颗粒均匀分散在浅色Ni(OH)2纳米线上，对Pt纳米颗粒进一步放大表征，可以看到其清晰的晶格条纹。对选定区域进一步进行傅里叶转换和反傅里叶转换后，轻易量取其条纹间距为0.227 nm与Pt（111）晶面对应，证明了Pt纳米颗粒的成功掺杂。在能谱图中可以看出，Ni和O元素在催化剂样品中的广泛和均匀分布，而Pt元素则只出现在亮白色颗粒区域。It can be seen from the figure that some Pt nanoparticles with a diameter of about 3.14 nm are firmly anchored in the Ni(OH)2 nanowire/sheet composite structure. The SAED diffraction pattern corresponds to the (100), (102) and (110) crystal planes of Ni(OH)2 and the (111) crystal plane of Pt, which is consistent with the XRD results. In the HRTEM image, it can be seen that the dark Pt nanoparticles are evenly dispersed on the light Ni(OH)2 nanowires, and further enlarged characterization of the Pt nanoparticles can be seen with clear lattice fringes. After further Fourier transform and inverse Fourier transform of the selected area, the fringe spacing of 0.227 nm was easily measured, corresponding to the Pt (111) crystal plane, which proved the successful doping of Pt nanoparticles. It can be seen in the energy spectrum that Ni and O elements are widely and uniformly distributed in the catalyst sample, while Pt elements only appear in the bright white particle area.
2. 电解水催化性能测试2. Catalytic Performance Test of Electrolyzed Water
对催化剂进行电解水催化性能评价，测试方法：采用环盘电极三电极系统进行循环伏安测试，三电极系统中各实施例和对比例中制备的催化剂电极作为工作电极，Hg|HgO电极作为参比电极，碳棒作为对电极；双电极水分解系统以所测实施例的催化剂电极分别作为阳极和阴极，或以对比例6为阴极对比例7为阳极组装的双电级系统；测试电解液为1MKOH溶液，HER和OER测试前先在电解液中分别通入H2和O2 20 nim，以排除产物溶解在电解液中对性能的影响。The catalytic performance of the catalyst for electrolysis of water is evaluated. The test method is to use the ring-disk electrode three-electrode system for cyclic voltammetry test. The catalyst electrode prepared in each embodiment and comparative example in the three-electrode system is used as the working electrode, and the Hg|HgO electrode is used as the reference electrode. Compared with the electrode, the carbon rod is used as the counter electrode; the two-electrode water splitting system uses the catalyst electrode of the measured embodiment as the anode and the cathode respectively, or uses the comparative example 6 as the cathode and the comparative example 7 as the dual-level system assembled by the anode; the test electrolyte It is a 1M KOH solution, and H2 and O2 20nim were passed through the electrolyte before the HER and OER tests, in order to eliminate the influence of the product dissolved in the electrolyte on the performance.
LSV测试温度为室温25℃，扫描速率为5mV/s，电流密度-时间测试曲线在对应的电位下进行。The LSV test temperature is
EIS阻抗测试的频率范围为10 kHz-0.01 Hz。The frequency range of EIS impedance testing is 10 kHz-0.01 Hz.
所有的LSV曲线都经过了iR修正，且通过参比电极对应的可逆氢电极（RHE）换算得到，根据Nernst方程：All LSV curves have been corrected by iR and converted by the reversible hydrogen electrode (RHE) corresponding to the reference electrode, according to the Nernst equation:
E(RHE) =E(Hg|HgO) + 0.0591 × pH + 0.098 (V)E(RHE) =E(Hg|HgO) + 0.0591 × pH + 0.098 (V)
其中E(Hg|HgO)是相对Hg|HgO的测量电位，0.098 V是Hg|HgO在25℃的标准电位。WhereE(Hg|HgO) is the measured potential relative to Hg|HgO, and 0.098 V is the standard potential of Hg|HgO at 25 °C.
测试结果如下所示：The test results are as follows:
表2是电化学测试本发明实施例1-3和对比例1-7的样品HER在10 mA/cm2和100mA/cm2以及OER在100 mA/cm2和400 mA/cm2的过电势。Table 2 shows the overpotentials of HER at 10 mA/cm2 and 100 mA/cm2 and OER at 100 mA/cm2 and 400 mA/cm2 of the samples HER of Examples 1-3 of the present invention and Comparative Examples 1-7 by electrochemical test .
表2Table 2
图7是本发明实施例1-3和对比例1-6的催化剂电极以及所用基底的HER（a）极化曲线，（b）Tafel斜率曲线。Fig. 7 is the HER (a) polarization curve and (b) Tafel slope curve of the catalyst electrodes and substrates used in Examples 1-3 and Comparative Examples 1-6 of the present invention.
从表2和图7可以看出，当电流密度为10 mA/cm2和100 mA/cm2时，实施例1-3的HER过电势均不高于对比例1-6，其中实施例1的Pt-Ni(OH)2@NM都表现出最佳HER活性，过电势分别为31 mV和68 mV，结合图7中的（a）的极化曲线表明实施例1的HER催化活性最强，超过商业贵金属Pt/C@NM。同时实施例1-3的Tafel斜率均低于对比例1-6，其中实施例1具有最小的Tafel斜率（42 mV/dec），超过了Pt/C@NM的性能。最小的过电势代表产生同样的氢气的能耗更低，更低的Tafel斜率则对应更快的HER反应动力学。可见本发明的实施例可以提高电极的催化活性和催化反应速率。对比例1因为NF的电阻较大，同时其三维结构复杂，在强碱环境下结构容易坍塌，机械强度低，组装成测试系统会带来更多接触阻抗，与本发明实施例相比不利于催化反应进行。It can be seen from Table 2 and Figure 7 that when the current density is 10 mA/cm2 and 100 mA/cm2 , the HER overpotentials of Examples 1-3 are not higher than those of Comparative Examples 1-6, and Example 1 The Pt-Ni(OH)2 @NM exhibited the best HER activity, with overpotentials of 31 mV and 68 mV, respectively, combined with the polarization curves of (a) in Figure 7, it shows that Example 1 has the strongest HER catalytic activity , exceeding the commercial precious metal Pt/C@NM. At the same time, the Tafel slopes of Examples 1-3 are lower than those of Comparative Examples 1-6, and Example 1 has the smallest Tafel slope (42 mV/dec), exceeding the performance of Pt/C@NM. The smallest overpotential represents lower energy consumption to produce the same hydrogen, and lower Tafel slope corresponds to faster HER reaction kinetics. It can be seen that the embodiment of the present invention can improve the catalytic activity and catalytic reaction rate of the electrode. Comparative example 1 is because the resistance of NF is relatively large, and its three-dimensional structure is complex at the same time, the structure is easy to collapse in a strong alkali environment, and the mechanical strength is low, and the assembly into a test system will bring more contact resistance, which is not conducive to comparing with the embodiment of the present invention. The catalytic reaction proceeds.
图8是本发明实施例1-3和对比例1-5、7的催化剂电极以及所用基底的OER（a）极化曲线、（b）Tafel斜率曲线对比。Fig. 8 is a comparison of OER (a) polarization curves and (b) Tafel slope curves of the catalyst electrodes and substrates used in Examples 1-3 of the present invention and Comparative Examples 1-5, 7.
从表2和图8中可以看出，当电流密度为100 mA/cm2和400 mA/cm2时，实施例1的Pt-Ni(OH)2@NM过电势分别为269 mV和301 mV，同样表现出最佳的OER催化活性，电解水生成同样数量的氧气消耗的电压最小。实施例1具有最小的Tafel斜率（51 mV/dec），不仅低于对比例1-5，而且超过了商业标准贵金属催化剂电极RuO2@NM的OER催化性能。实施例2和3也表现出优于对比例1-5、7的OER催化性能。可见本发明的实施例可以提高电极的催化活性和催化反应速率。It can be seen from Table 2 and Figure 8 that when the current density is 100 mA/cm2 and 400 mA/cm2 , the overpotential of Pt-Ni(OH)2 @NM in Example 1 is 269 mV and 301 mV, respectively , also exhibited the best OER catalytic activity, and the electrolysis of water to generate the same amount of oxygen consumes the least voltage. Example 1 has the smallest Tafel slope (51 mV/dec), which is not only lower than Comparative Examples 1-5, but also exceeds the OER catalytic performance of the commercial standard noble metal catalyst electrode RuO2 @NM. Examples 2 and 3 also exhibit better OER catalytic performance than Comparative Examples 1-5, 7. It can be seen that the embodiment of the present invention can improve the catalytic activity and catalytic reaction rate of the electrode.
图9 是本发明实施例1的全水解三电极系统化曲线（a）、实施例1组合、对比例6和对比例7组合组装的全水解双电级系统极化曲线（b）；Figure 9 is the full hydrolysis three-electrode systematization curve (a) of Example 1 of the present invention, the polarization curve (b) of the full hydrolysis double-electrode system assembled by the combination of Example 1, Comparative Example 6 and Comparative Example 7;
从图中可以看出，实施例1所需的∆V（∆V =VOER -VHER）为1.53 V和1.57 V，以驱动水分解反应达到50 mA/cm2和100 mA/cm2。接着，用Pt-Ni(OH)2@NM分别作为阳极和阴极构建了一个双电极水分解系统（Pt-Ni(OH)2@NM || Pt-Ni(OH)2@NM）。与对比例6和对比例7组装的双电级系统Pt/C@NM || RuO2@NM进行比较，Pt-Ni(OH)2@NM || Pt-Ni(OH)2@NM系统需要1.491 V和1.652 V即可达到10 mA/cm2和100 mA/cm2，优于Pt/C@NM || RuO2@NM组合（E10= 1.553 V，E100 = 1.736 V）。It can be seen from the figure that the∆V (∆V =VOER −VHER ) required by Example 1 is 1.53 V and 1.57 V to drive the water splitting reaction to 50 mA/cm2 and 100 mA/cm2 . Next, a two-electrode water splitting system (Pt-Ni(OH)2 @NM || Pt-Ni(OH)2 @NM) was constructed using Pt-Ni(OH)2 @NM as the anode and cathode, respectively. Compared with the two-level system Pt/C@NM || RuO2 @NM assembled in Comparative Example 6 and Comparative Example 7, the Pt-Ni(OH)2 @NM || Pt-Ni(OH)2 @NM system requires 1.491 V and 1.652 V can reach 10 mA/cm2 and 100 mA/cm2 , which is better than Pt/C@NM || RuO2 @NM combination (E10 = 1.553 V,E100 = 1.736 V).
图10是本发明实施例1 Pt-Ni(OH)2@NM的（a）HER，（b）OER和（c）全水解双电级系统测试的循环寿命曲线，插图为恒电位测试曲线。Figure 10 is the cycle life curves of (a) HER, (b) OER and (c) full hydrolysis dual-level system tests of Pt-Ni(OH)2 @NM in Example 1 of the present invention, and the inset is the potentiostatic test curve.
从图中可以看出，Pt-Ni(OH)2@NM在经过10000圈CV循环后，其极化曲线与初始相比基本重合，而在经过40 h的HER和OER恒电位测试后，其电流密度分别保留为初始状态的99.3%和98.5%，经过100 h的全水解恒电位测试后，电流密度保持为初始状态的96.6%。It can be seen from the figure that after 10,000 CV cycles, the polarization curves of Pt-Ni(OH)2 @NM basically coincide with the initial ones, and after 40 h of HER and OER constant potential tests, its The current density remained at 99.3% and 98.5% of the initial state, respectively, and after 100 h of full hydrolysis potentiostatic test, the current density remained at 96.6% of the initial state.
图11是本发明实施例1 Pt-Ni(OH)2@NM、实施例1的基底NM，对比例1 Pt-Ni(OH)2@NF以及对比例6、7的组合（Pt/C@NM || RuO2@NM）组装到碱性水电解槽的（a）电解槽结构示意图，（b）极化曲线，（c）400 mA/cm2和1000 mA/cm2的电压对比图，（d）阻抗图；实施例1的催化剂电极和基底的成本、电压消耗对比图（e）；实施例1和对比例1在80℃下400 mA/cm2的电压-时间曲线（f）。Figure 11 is the combination of Example 1 Pt-Ni(OH)2 @NM of the present invention, the substrate NM of Example 1, Comparative Example 1 Pt-Ni(OH)2 @NF and Comparative Examples 6 and 7 (Pt/C@ NM || RuO2 @NM) assembled into an alkaline water electrolyzer (a) Schematic diagram of the electrolyzer structure, (b) Polarization curve, (c) Voltage comparison diagram of 400 mA/cm2 and 1000 mA/cm2 , (d) Impedance diagram; cost and voltage consumption comparison diagram (e) of catalyst electrode and substrate of Example 1; voltage-time curve (f) of Example 1 and Comparative Example 1 at 80 °C at 400 mA/cm2 .
从图中可以看出，Pt-Ni(OH)2@NM在组装到碱性水电解槽后仍表现出最小的电位需求，达到400 mA/cm2和1000 mA/m2的仅需要1.87 V和2.24 V，优于Pt/C@NM || RuO2@NM电极；Pt-Ni(OH)2@NF达到400 mA/cm2和1000 mA/cm2的电位也比Pt/C@NM || RuO2@NM电极的电位低；说明本发明的实施例电解水生成同样数量的氢气和氧气所需要消耗的电压小，能量利用效率高。与商业标准贵金属组合对比，本发明的实施例可以在保证电解效果更好的前提下成功降低成本。相比纯NM，成本仅高了0.013 元/cm2，而达到1000 mA/cm2的所需电压减少了0.84 V。通过阻抗图可以看出，Pt-Ni(OH)2@NM具备最小的接触电阻（仅为0.23 Ω）。恒电流测试曲线展示了，在400 mA/cm2的电流密度下，Pt-Ni(OH)2@NM在600 h中的电压增加率仅为0.13 mV/h1，可以看出Pt-Ni(OH)2@NM催化电极的稳定性非常好。It can be seen from the figure that Pt-Ni(OH)2 @NM still exhibits the minimum potential demand after being assembled into the alkaline water electrolyzer, and only 1.87 V is needed to reach 400 mA/cm2 and 1000 mA/m2 and 2.24 V, betterthan Pt/C@NM || RuO2@NM electrodes; The potential of the RuO2 @NM electrode is low; it shows that the embodiment of the present invention electrolyzes water to generate the same amount of hydrogen and oxygen, which requires a small voltage consumption and high energy utilization efficiency. Compared with the commercial standard precious metal combination, the embodiment of the present invention can successfully reduce the cost under the premise of ensuring better electrolysis effect. Compared with pure NM, the cost is only 0.013 yuan/cm2 higher, and the required voltage to reach 1000 mA/cm2 is reduced by 0.84 V. It can be seen from the impedance diagram that Pt-Ni(OH)2 @NM has the smallest contact resistance (only 0.23 Ω). The galvanostatic test curve shows that at a current density of 400 mA/cm2 , the voltage increase rate of Pt-Ni(OH)2 @NM in 600 h is only 0.13 mV/h1 , it can be seen that Pt-Ni( OH)2 @NM catalytic electrode is very stable.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Apparently, the above-mentioned embodiments are only examples for clear description, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. And the obvious changes or changes derived therefrom are still within the scope of protection of the present invention.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2727852A1 (en)* | 1977-06-21 | 1979-01-18 | Siemens Ag | Electrode contg. bismuth and platinum metals - for electrochemical oxidn. of hydrocarbon(s) contg. hydroxyl gps., esp. in fuel cells |
| US6689505B1 (en)* | 1999-08-27 | 2004-02-10 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Electrocatalyst for fuel cells |
| CN105826573A (en)* | 2016-05-12 | 2016-08-03 | 湖北大学 | Surface treatment method for improving electro-catalysis hydrogen production performance |
| EP3553866A1 (en)* | 2018-04-13 | 2019-10-16 | Technische Universität Berlin | Catalyst material for a fuel cell, and method of producing the same |
| CN113026031A (en)* | 2021-02-25 | 2021-06-25 | 澳门大学 | Electrode material, preparation method and application thereof, and assembled water electrolysis device |
| US20210220803A1 (en)* | 2020-01-22 | 2021-07-22 | The Regents Of The University Of California | Carbon-doped nickel oxide catalyst and methods for making and using thereof |
| CN113174600A (en)* | 2021-04-22 | 2021-07-27 | 佛山仙湖实验室 | Porous nickel screen electrolytic water catalytic material and preparation method thereof |
| CN114016067A (en)* | 2021-12-03 | 2022-02-08 | 北京科技大学 | A kind of preparation method of self-supporting bifunctional water electrolysis catalyst |
- 2022
- 2022-12-19CNCN202211629480.9Apatent/CN115627493A/enactivePending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2727852A1 (en)* | 1977-06-21 | 1979-01-18 | Siemens Ag | Electrode contg. bismuth and platinum metals - for electrochemical oxidn. of hydrocarbon(s) contg. hydroxyl gps., esp. in fuel cells |
| US6689505B1 (en)* | 1999-08-27 | 2004-02-10 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Electrocatalyst for fuel cells |
| CN105826573A (en)* | 2016-05-12 | 2016-08-03 | 湖北大学 | Surface treatment method for improving electro-catalysis hydrogen production performance |
| EP3553866A1 (en)* | 2018-04-13 | 2019-10-16 | Technische Universität Berlin | Catalyst material for a fuel cell, and method of producing the same |
| US20210220803A1 (en)* | 2020-01-22 | 2021-07-22 | The Regents Of The University Of California | Carbon-doped nickel oxide catalyst and methods for making and using thereof |
| CN113026031A (en)* | 2021-02-25 | 2021-06-25 | 澳门大学 | Electrode material, preparation method and application thereof, and assembled water electrolysis device |
| CN113174600A (en)* | 2021-04-22 | 2021-07-27 | 佛山仙湖实验室 | Porous nickel screen electrolytic water catalytic material and preparation method thereof |
| CN114016067A (en)* | 2021-12-03 | 2022-02-08 | 北京科技大学 | A kind of preparation method of self-supporting bifunctional water electrolysis catalyst |
Non-Patent Citations (1)
| Title |
|---|
| JUNYUZHANG等: "Ultra-low Pt-loaded catalyst based on nickel mesh for boosting alkaline water electrolysis"* |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116219476A (en)* | 2023-02-20 | 2023-06-06 | 北京化工大学 | A two-dimensional nickel-based sulfide-supported Pt single-atom catalyst and its preparation method |
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