技术领域Technical field
本发明涉及催化材料技术领域，具体是一种原子掺杂策略构筑的高效电解水催化剂及其制备方法和应用。The invention relates to the technical field of catalytic materials, specifically a high-efficiency electrolysis water catalyst constructed with an atomic doping strategy and its preparation method and application.
背景技术Background technique
电解水技术是一种高效、清洁、高纯的制氢技术。水分解由两个半反应组成：析氢（HER）和析氧（OER）。其中，OER 是一种四-电子-质子偶联反应，其反应过程复杂，需要更高的能量（更高的过电位）来克服反应势垒。因此，缓慢的 OER 动力学是阻碍整体水分解应用的关键问题之一。在目前，RuO2 或 IrO2 等电催化剂有效地降低了 OER 活化势垒并促进了反应过程。然而，这些贵金属电催化剂的高成本限制了它们的商业应用。因此，非常有必要采用更经济和丰富的非贵金属基化合物作为电解水分解催化剂。例如，氧化物、氢氧化物、层状双氢氧化物 (LDH)、金属有机框架(MOF) 等。LDH 是基于带正电荷的层状结构，层间有阴离子和水分子。这种层状结构可以使溶液充分包裹住催化剂，进行充分反应。Water electrolysis technology is an efficient, clean and high-purity hydrogen production technology. Water splitting consists of two half-reactions: hydrogen evolution (HER) and oxygen evolution (OER). Among them, OER is a four-electron-proton coupling reaction with a complex reaction process that requires higher energy (higher overpotential) to overcome the reaction barrier. Therefore, slow OER kinetics is one of the key issues hindering overall water splitting applications. At present, electrocatalysts such as RuO2 or IrO2 effectively lower the OER activation barrier and promote the reaction process. However, the high cost of these noble metal electrocatalysts limits their commercial applications. Therefore, it is highly necessary to adopt more economical and abundant non-noble metal-based compounds as electrolytic water splitting catalysts. For example, oxides, hydroxides, layered double hydroxides (LDH), metal organic frameworks (MOF), etc. LDH is based on a positively charged layered structure with anions and water molecules between the layers. This layered structure allows the solution to fully wrap the catalyst and carry out a full reaction.
在这些非贵金属电催化剂中，CoMn-LDH 因其优异的 OER 性能在候选材料中脱颖而出，已被广泛研究作为 OER 催化剂。然而，由于 Mn 和 Co 的层间位置的不同而导致的晶格失配会引起电荷转移电阻的增加，从而阻碍反应的继续进行。目前，原子掺杂策略已成为一种流行的策略来调控电子分布，这有利于优化反应中间体的吸附能，从而提高水分解效率。因此在这里，我们提出了一种通过原子掺杂策略在柔性碳纤维布上制备具有晶格缺陷的蜂巢结构 N@CoMn-LDH/CC 电化学水分解催化剂的新方法，这种结构可以使电解液得到充分浸润，极大地降低电荷转移电阻。Among these non-noble metal electrocatalysts, CoMn-LDH stands out among candidate materials due to its excellent OER performance and has been widely studied as an OER catalyst. However, the lattice mismatch due to the different interlayer positions of Mn and Co can cause an increase in charge transfer resistance, thus hindering the reaction from proceeding. Currently, the atomic doping strategy has become a popular strategy to regulate electron distribution, which is beneficial to optimizing the adsorption energy of reaction intermediates and thereby improving water splitting efficiency. Therefore here, we propose a new method to prepare honeycomb structure N@CoMn-LDH/CC electrochemical water splitting catalyst with lattice defects on flexible carbon fiber cloth through atomic doping strategy. This structure can make the electrolyte Be fully wetted and greatly reduce the charge transfer resistance.
发明内容Contents of the invention
本发明的目的是为了克服现有技术存在的缺点和不足，而提供一种原子掺杂策略构筑的高效电解水催化剂及其制备方法，本发明所采取的技术方案如下：The purpose of the present invention is to overcome the shortcomings and deficiencies of the existing technology and provide an efficient electrolysis water catalyst constructed with an atomic doping strategy and a preparation method thereof. The technical solutions adopted by the present invention are as follows:
第一方面，提供一种原子掺杂策略构筑的高效电解水催化剂的制备方法，包括以下步骤：In the first aspect, a method for preparing a high-efficiency water electrolysis catalyst constructed with an atomic doping strategy is provided, including the following steps:
步骤一：将2-甲基咪唑溶液快速加入硝酸钴六水合物溶液中，形成蓝紫色悬浮液，随后，将一块碳布浸泡在该溶液中，并在室温下放置。反应结束后，取出ZIF/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥备用；Step 1: Quickly add the 2-methylimidazole solution to the cobalt nitrate hexahydrate solution to form a blue-purple suspension. Then, soak a piece of carbon cloth in the solution and leave it at room temperature. After the reaction is completed, take out the ZIF/CC, wash it several times with deionized water, and dry it in an oven at 60°C for later use;
步骤二：将含锰化合物溶解在去离子水中以形成澄清溶液，随后，将ZIF浸泡在上述溶液中，反应结束后，取出CoMn-LDH/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥备用；Step 2: Dissolve the manganese-containing compound in deionized water to form a clear solution. Then, soak the ZIF in the above solution. After the reaction is completed, take out the CoMn-LDH/CC, wash it several times with deionized water, and incubate it at 60°C. Dry in the oven and set aside;
步骤三：将CoMn-LDH/CC放置在温度可控的ALD室中，使用一定功率并暴露于氮等离子体中，在等离子体氮化过程中，保持一定的工作压力保持和氮气流速。Step 3: Place the CoMn-LDH/CC in a temperature-controlled ALD chamber, use a certain power and expose it to nitrogen plasma. During the plasma nitriding process, maintain a certain working pressure and nitrogen flow rate.
作为优选，步骤一中，2-甲基咪唑的质量为600-900 mg，硝酸钴六水合物的质量为250-400 mg，时间为6-12 h。反应结束后得到钴的ZIF，标记为Co-ZIF/CC；Preferably, in step one, the mass of 2-methylimidazole is 600-900 mg, the mass of cobalt nitrate hexahydrate is 250-400 mg, and the time is 6-12 h. After the reaction is completed, the ZIF of cobalt is obtained, labeled Co-ZIF/CC;
步骤二中，氯化锰的质量为60-100 mg，溶液体积为20-80 ml，时间为2-12h，反应结束后得到CoMn-LDH/CC；In step two, the mass of manganese chloride is 60-100 mg, the solution volume is 20-80 ml, and the time is 2-12 hours. After the reaction is completed, CoMn-LDH/CC is obtained;
步骤二中，含锰化合物，即锰的来源可以为氯化锰、高锰酸盐、锰酸盐其中任一种或多种；In step two, the manganese-containing compound, that is, the source of manganese, can be any one or more of manganese chloride, permanganate, and manganate;
步骤三中，ALD室温度为160-240 ℃，功率为250-750 W，时间为15-45s（时间最优选为30s），压力为0.58-0.98 mbar，氮气流速为50-150 sccm，得到最终产物N@CoMn-LDH/CC。In step three, the ALD chamber temperature is 160-240 ℃, the power is 250-750 W, the time is 15-45s (the most preferred time is 30s), the pressure is 0.58-0.98 mbar, and the nitrogen flow rate is 50-150 sccm to obtain the final Product N@CoMn-LDH/CC.
第二方面，还包括上述制备方法制备得到高效电催化剂，作为优选，所述的高效电催化剂应用于碱性条件下电解水。The second aspect also includes the above preparation method to prepare a high-efficiency electrocatalyst. Preferably, the high-efficiency electrocatalyst is used for electrolysis of water under alkaline conditions.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
1. 本发明采用将2-甲基咪唑，六水合硝酸钴和氯化锰溶液在常温下浸泡的方法，在碳布上生长钴锰双层氢氧化物材料，然后经过氮等离子体掺杂，最终形成具有蜂巢结构的纳米片多孔结构，这种具有晶格缺陷的结构增加了活性表面积，从而提高电子传输速率以及增加对析氧反应中间体的吸附能力；碳布提供一个三维结构，有利于增加材料的导电性；1. The present invention adopts the method of soaking 2-methylimidazole, cobalt nitrate hexahydrate and manganese chloride solution at normal temperature to grow a cobalt-manganese double-layer hydroxide material on carbon cloth, and then doping with nitrogen plasma. Finally, a nanosheet porous structure with a honeycomb structure is formed. This structure with lattice defects increases the active surface area, thereby increasing the electron transmission rate and increasing the adsorption capacity for oxygen evolution reaction intermediates; the carbon cloth provides a three-dimensional structure, which is beneficial to Increase the conductivity of materials;
2. 本发明的催化剂中的氮原子具有良好的配位能力，可对中心原子的电子结构进行大幅调控，充分发挥每个活性位点的催化性能，更有助于水分子的解离和氢的脱附，也能提高催化剂的稳定性。2. The nitrogen atoms in the catalyst of the present invention have good coordination ability, which can greatly regulate the electronic structure of the central atom, give full play to the catalytic performance of each active site, and further contribute to the dissociation of water molecules and hydrogenation. Desorption can also improve the stability of the catalyst.
附图说明Description of the drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例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，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，根据这些附图获得其他的附图仍属于本发明的范畴。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are only These are some embodiments of the present invention. For those of ordinary skill in the art, it is still within the scope of the present invention to obtain other drawings based on these drawings without exerting any creative effort.
图1为实施例1中CoMn-LDH/CC和N@CoMn-LDH/CC的扫描电镜图，从图中可以看出经过掺杂后的CoMn-LDH/CC表面变的粗糙，逐渐形成蜂窝状的结构，证明氮原子成功掺杂进CoMn-LDH/CC；Figure 1 is a scanning electron microscope image of CoMn-LDH/CC and N@CoMn-LDH/CC in Example 1. It can be seen from the figure that the surface of CoMn-LDH/CC after doping becomes rough and gradually forms a honeycomb shape. The structure proves that nitrogen atoms are successfully doped into CoMn-LDH/CC;
图2为实施例1、2、3中Co-ZIF/CC、CoMn-LDH/CC和N@CoMn-LDH/CC的XRD图，从图中可以看出N@CoMn-LDH/CC相对于CoMn-LDH/CC的衍射峰发生了偏移，说明电沉积的N原子对CoMn-LDH/CC起到了调控作用；Figure 2 is the XRD pattern of Co-ZIF/CC, CoMn-LDH/CC and N@CoMn-LDH/CC in Examples 1, 2 and 3. From the figure, it can be seen that N@CoMn-LDH/CC is relatively better than CoMn The diffraction peak of -LDH/CC has shifted, indicating that the electrodeposited N atoms play a regulatory role in CoMn-LDH/CC;
图3为实施例1、4的线性循环曲线图和双电层电容图，从图中可以看出含N的催化剂比不含N的催化剂在电解水析氧中的表现更加优异；Figure 3 is the linear cycle curve and double-layer capacitance diagram of Examples 1 and 4. It can be seen from the figure that the N-containing catalyst performs better in the electrolysis of water for oxygen evolution than the N-free catalyst;
图4为实施例1、5、6、7的的线性循环曲线图和过电位图，从图中可以看出最佳的氮掺杂时间为30s；Figure 4 shows the linear cycle curves and overpotential diagrams of Examples 1, 5, 6 and 7. It can be seen from the figure that the optimal nitrogen doping time is 30s;
图5为实施例1、5、6、7的双电层电容图，从图中可以进一步看出氮掺杂时间为30s的催化性能最高。Figure 5 is a double-layer capacitance diagram of Examples 1, 5, 6, and 7. From the figure, it can be further seen that the catalytic performance of the nitrogen doping time of 30 seconds is the highest.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面将结合附图和实施例对本发明作进一步地详细描述，其目的在于更好的理解本发明的技术内涵，但并不限制本发明。In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail below in conjunction with the drawings and examples. The purpose is to better understand the technical connotation of the present invention, but it does not limit the present invention.
实施例1：Example 1:
样品制备：将20mL 2-甲基咪唑（790 mg）溶液快速加入20mL硝酸钴六水合物（326mg）溶液中，形成蓝紫色悬浮液。随后，将一块清洗干净的2*3 cm的碳布浸泡在该溶液中，并在室温下放置8小时。反应结束后，取出Co-ZIF/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将82mg MnCl2溶解在40mL去离子水中以形成澄清溶液。随后，将Co-ZIF/CC在上述溶液中浸泡2小时。反应结束后，取出CoMn-LDH/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将CoMn-LDH/CC在200°C的典型ALD室中暴露于500 W的氮等离子体中30 s。在等离子体氮化过程中，工作压力保持在0.78mbar，氮气流速为100sccm，得到原子掺杂策略构筑的高效电催化剂N@CoMn-LDH/CC。Sample preparation: quickly add 20 mL of 2-methylimidazole (790 mg) solution to 20 mL of cobalt nitrate hexahydrate (326 mg) solution to form a blue-violet suspension. Subsequently, a cleaned 2*3 cm carbon cloth was soaked in the solution and left at room temperature for 8 hours. After the reaction, the Co-ZIF/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. Dissolve82 mg of MnCl in 40 mL of deionized water to form a clear solution. Subsequently, Co-ZIF/CC was soaked in the above solution for 2 hours. After the reaction, the CoMn-LDH/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. The CoMn-LDH/CC was exposed to 500 W nitrogen plasma for 30 s in a typical ALD chamber at 200 °C. During the plasma nitridation process, the working pressure was maintained at 0.78 mbar, and the nitrogen flow rate was 100 sccm. A high-efficiency electrocatalyst N@CoMn-LDH/CC constructed with an atomic doping strategy was obtained.
电催化应用：以上述制备的N@CoMn-LDH/CC纳米材料为工作电极，在三电极体系（铂丝电极作为对电极，饱和Ag/AgCl电极作为参比电极）中，以1 M KOH溶液为电解质溶液测量催化剂的线性扫描伏安曲线。产氧时该样品电流密度为10 mAcm-2时，过电位为238 mV。此样品电催化性能最佳。Electrocatalytic application: Using the N@CoMn-LDH/CC nanomaterial prepared above as the working electrode, in a three-electrode system (platinum wire electrode as the counter electrode, saturated Ag/AgCl electrode as the reference electrode), 1 M KOH solution The linear sweep voltammetry curve of the catalyst was measured for the electrolyte solution. When oxygen is produced, the overpotential of this sample is 238 mV when the current density is 10 mAcm-2 . This sample has the best electrocatalytic performance.
实施例2：Example 2:
样品制备：将20mL 2-甲基咪唑（800 mg）溶液快速加入20mL硝酸钴六水合物（326mg）溶液中，形成蓝紫色悬浮液。随后，将一块清洗干净的2*3 cm的碳布浸泡在该溶液中，并在室温下放置8小时。反应结束后，取出Co-ZIF/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将82mg MnCl2溶解在40mL去离子水中以形成澄清溶液。随后，将Co-ZIF/CC在上述溶液中浸泡2小时。反应结束后，取出CoMn-LDH/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将CoMn-LDH/CC在200°C的典型ALD室中暴露于500 W的氮等离子体中30 s。在等离子体氮化过程中，工作压力保持在0.78 mbar，氮气流速为100 sccm，得到原子掺杂策略构筑的高效电催化剂N@CoMn-LDH/CC。Sample preparation: quickly add 20 mL of 2-methylimidazole (800 mg) solution to 20 mL of cobalt nitrate hexahydrate (326 mg) solution to form a blue-violet suspension. Subsequently, a cleaned 2*3 cm carbon cloth was soaked in the solution and left at room temperature for 8 hours. After the reaction, the Co-ZIF/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. Dissolve82 mg of MnCl in 40 mL of deionized water to form a clear solution. Subsequently, Co-ZIF/CC was soaked in the above solution for 2 hours. After the reaction, the CoMn-LDH/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. The CoMn-LDH/CC was exposed to 500 W nitrogen plasma for 30 s in a typical ALD chamber at 200 °C. During the plasma nitridation process, the working pressure was maintained at 0.78 mbar, and the nitrogen flow rate was 100 sccm. An efficient electrocatalyst N@CoMn-LDH/CC constructed with an atomic doping strategy was obtained.
电催化应用：制备电极及测试同实例1。该样品电流密度为10 mA cm-2时，析氧过电位为276 mV。Electrocatalytic application: Preparation of electrodes and testing are the same as Example 1. When the current density of this sample is 10 mA cm-2 , the oxygen evolution overpotential is 276 mV.
实施例3：Example 3:
样品制备：将20mL 2-甲基咪唑（790 mg）溶液快速加入20mL硝酸钴六水合物（346mg）溶液中，形成蓝紫色悬浮液。随后，将一块清洗干净的2*3 cm的碳布浸泡在该溶液中，并在室温下放置8小时。反应结束后，取出Co-ZIF/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将82mg MnCl2溶解在40mL去离子水中以形成澄清溶液。随后，将Co-ZIF/CC在上述溶液中浸泡2小时。反应结束后，取出CoMn-LDH/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将CoMn-LDH/CC在200°C的典型ALD室中暴露于500 W的氮等离子体中30 s。在等离子体氮化过程中，工作压力保持在0.78 mbar，氮气流速为100 sccm，得到原子掺杂策略构筑的高效电催化剂N@CoMn-LDH/CC。Sample preparation: quickly add 20 mL of 2-methylimidazole (790 mg) solution to 20 mL of cobalt nitrate hexahydrate (346 mg) solution to form a blue-violet suspension. Subsequently, a cleaned 2*3 cm carbon cloth was soaked in the solution and left at room temperature for 8 hours. After the reaction, the Co-ZIF/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. Dissolve82 mg of MnCl in 40 mL of deionized water to form a clear solution. Subsequently, Co-ZIF/CC was soaked in the above solution for 2 hours. After the reaction, the CoMn-LDH/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. The CoMn-LDH/CC was exposed to 500 W nitrogen plasma for 30 s in a typical ALD chamber at 200 °C. During the plasma nitridation process, the working pressure was maintained at 0.78 mbar, and the nitrogen flow rate was 100 sccm. An efficient electrocatalyst N@CoMn-LDH/CC constructed with an atomic doping strategy was obtained.
电催化应用：制备电极及测试同实例1。该样品电流密度为10 mA cm-2时，析氧的过电位为298 mV。Electrocatalytic application: Preparation of electrodes and testing are the same as Example 1. When the current density of this sample is 10 mA cm-2 , the overpotential of oxygen evolution is 298 mV.
实施例4：Example 4:
样品制备：将20mL 2-甲基咪唑（790 mg）溶液快速加入20mL硝酸钴六水合物（326mg）溶液中，形成蓝紫色悬浮液。随后，将一块清洗干净的2*3 cm的碳布浸泡在该溶液中，并在室温下放置8小时。反应结束后，取出Co-ZIF/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将82mg MnCl2溶解在40mL去离子水中以形成澄清溶液。随后，将Co-ZIF/CC在上述溶液中浸泡2小时。反应结束后，取出CoMn-LDH/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。Sample preparation: quickly add 20 mL of 2-methylimidazole (790 mg) solution to 20 mL of cobalt nitrate hexahydrate (326 mg) solution to form a blue-violet suspension. Subsequently, a cleaned 2*3 cm carbon cloth was soaked in the solution and left at room temperature for 8 hours. After the reaction, the Co-ZIF/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. Dissolve82 mg of MnCl in 40 mL of deionized water to form a clear solution. Subsequently, Co-ZIF/CC was soaked in the above solution for 2 hours. After the reaction, the CoMn-LDH/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C.
电催化应用：制备电极及测试同实例1。该样品电流密度为10 mA cm-2时，析氧的过电位为318 mV。Electrocatalytic application: Preparation of electrodes and testing are the same as Example 1. When the current density of this sample is 10 mA cm-2 , the overpotential of oxygen evolution is 318 mV.
实施例5：Example 5:
样品制备：将20mL 2-甲基咪唑（790 mg）溶液快速加入20mL硝酸钴六水合物（326mg）溶液中，形成蓝紫色悬浮液。随后，将一块清洗干净的2*3 cm的碳布浸泡在该溶液中，并在室温下放置8小时。反应结束后，取出Co-ZIF/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将82mg MnCl2溶解在40mL去离子水中以形成澄清溶液。随后，将Co-ZIF/CC在上述溶液中浸泡2小时。反应结束后，取出CoMn-LDH/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将CoMn-LDH/CC在200°C的典型ALD室中暴露于500 W的氮等离子体中15 s。在等离子体氮化过程中，工作压力保持在0.78 mbar，氮气流速为100 sccm，得到原子掺杂策略构筑的高效电催化剂N@CoMn-LDH/CC。Sample preparation: quickly add 20 mL of 2-methylimidazole (790 mg) solution to 20 mL of cobalt nitrate hexahydrate (326 mg) solution to form a blue-violet suspension. Subsequently, a cleaned 2*3 cm carbon cloth was soaked in the solution and left at room temperature for 8 hours. After the reaction, the Co-ZIF/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. Dissolve82 mg of MnCl in 40 mL of deionized water to form a clear solution. Subsequently, Co-ZIF/CC was soaked in the above solution for 2 hours. After the reaction, the CoMn-LDH/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. The CoMn-LDH/CC was exposed to 500 W nitrogen plasma in a typical ALD chamber at 200 °C for 15 s. During the plasma nitridation process, the working pressure was maintained at 0.78 mbar, and the nitrogen flow rate was 100 sccm. An efficient electrocatalyst N@CoMn-LDH/CC constructed with an atomic doping strategy was obtained.
电催化应用：制备电极及测试同实例1。该样品电流密度为10 mA cm-2时，析氧的过电位为300 mV。Electrocatalytic application: Preparation of electrodes and testing are the same as Example 1. When the current density of this sample is 10 mA cm-2 , the overpotential of oxygen evolution is 300 mV.
实施例6：Example 6:
样品制备：将20mL 2-甲基咪唑（790 mg）溶液快速加入20mL硝酸钴六水合物（326mg）溶液中，形成蓝紫色悬浮液。随后，将一块清洗干净的2*3 cm的碳布浸泡在该溶液中，并在室温下放置8小时。反应结束后，取出Co-ZIF/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将82mg MnCl2溶解在40mL去离子水中以形成澄清溶液。随后，将Co-ZIF/CC在上述溶液中浸泡2小时。反应结束后，取出CoMn-LDH/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将CoMn-LDH/CC在200°C的典型ALD室中暴露于500 W的氮等离子体中60 s。在等离子体氮化过程中，工作压力保持在0.78 mbar，氮气流速为100 sccm，得到原子掺杂策略构筑的高效电催化剂N@CoMn-LDH/CC。Sample preparation: quickly add 20 mL of 2-methylimidazole (790 mg) solution to 20 mL of cobalt nitrate hexahydrate (326 mg) solution to form a blue-violet suspension. Subsequently, a cleaned 2*3 cm carbon cloth was soaked in the solution and left at room temperature for 8 hours. After the reaction, the Co-ZIF/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. Dissolve82 mg of MnCl in 40 mL of deionized water to form a clear solution. Subsequently, Co-ZIF/CC was soaked in the above solution for 2 hours. After the reaction, the CoMn-LDH/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. The CoMn-LDH/CC was exposed to 500 W nitrogen plasma for 60 s in a typical ALD chamber at 200 °C. During the plasma nitridation process, the working pressure was maintained at 0.78 mbar, and the nitrogen flow rate was 100 sccm. An efficient electrocatalyst N@CoMn-LDH/CC constructed with an atomic doping strategy was obtained.
电催化应用：制备电极及测试同实例1。该样品电流密度为10 mA cm-2时，析氧的过电位为325 mV。Electrocatalytic application: Preparation of electrodes and testing are the same as Example 1. When the current density of this sample is 10 mA cm-2 , the overpotential of oxygen evolution is 325 mV.
实施例7：Example 7:
样品制备：将20mL 2-甲基咪唑（790 mg）溶液快速加入20mL硝酸钴六水合物（326mg）溶液中，形成蓝紫色悬浮液。随后，将一块清洗干净的2*3 cm的碳布浸泡在该溶液中，并在室温下放置8小时。反应结束后，取出Co-ZIF/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将82mg MnCl2溶解在40mL去离子水中以形成澄清溶液。随后，将Co-ZIF/CC在上述溶液中浸泡2小时。反应结束后，取出CoMn-LDH/CC，用去离子水洗涤数次，并在60℃的烘箱中干燥。将CoMn-LDH/CC在200°C的典型ALD室中暴露于500 W的氮等离子体中90 s。在等离子体氮化过程中，工作压力保持在0.78 mbar，氮气流速为100 sccm，得到原子掺杂策略构筑的高效电催化剂N@CoMn-LDH/CC。Sample preparation: quickly add 20 mL of 2-methylimidazole (790 mg) solution to 20 mL of cobalt nitrate hexahydrate (326 mg) solution to form a blue-violet suspension. Subsequently, a cleaned 2*3 cm carbon cloth was soaked in the solution and left at room temperature for 8 hours. After the reaction, the Co-ZIF/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. Dissolve82 mg of MnCl in 40 mL of deionized water to form a clear solution. Subsequently, Co-ZIF/CC was soaked in the above solution for 2 hours. After the reaction, the CoMn-LDH/CC was taken out, washed several times with deionized water, and dried in an oven at 60°C. The CoMn-LDH/CC was exposed to 500 W nitrogen plasma in a typical ALD chamber at 200 °C for 90 s. During the plasma nitridation process, the working pressure was maintained at 0.78 mbar, and the nitrogen flow rate was 100 sccm. An efficient electrocatalyst N@CoMn-LDH/CC constructed with an atomic doping strategy was obtained.
电催化应用：制备电极及测试同实例1，该样品电流密度为10 mA cm-2时，析氧过电位为356 mV。Electrocatalytic application: The electrode preparation and testing are the same as Example 1. When the current density of this sample is 10 mA cm-2 , the oxygen evolution overpotential is 356 mV.
上述实施例测试结果如图1-5所示：The test results of the above embodiment are shown in Figure 1-5:
图1为实施例1中CoMn-LDH/CC和N@CoMn-LDH/CC的扫描电镜图，从图中可以看出经过掺杂后的CoMn-LDH/CC表面变的粗糙，逐渐形成蜂窝状的结构，证明氮原子成功掺杂进CoMn-LDH/CC；Figure 1 is a scanning electron microscope image of CoMn-LDH/CC and N@CoMn-LDH/CC in Example 1. It can be seen from the figure that the surface of CoMn-LDH/CC after doping becomes rough and gradually forms a honeycomb shape. The structure proves that nitrogen atoms are successfully doped into CoMn-LDH/CC;
图2为实施例1、2、3中Co-ZIF/CC、CoMn-LDH/CC和N@CoMn-LDH/CC的XRD图，从图中可以看出N@CoMn-LDH/CC相对于CoMn-LDH/CC的衍射峰发生了偏移，说明电沉积的N原子对CoMn-LDH/CC起到了调控作用；Figure 2 is the XRD pattern of Co-ZIF/CC, CoMn-LDH/CC and N@CoMn-LDH/CC in Examples 1, 2 and 3. From the figure, it can be seen that N@CoMn-LDH/CC is relatively better than CoMn The diffraction peak of -LDH/CC has shifted, indicating that the electrodeposited N atoms play a regulatory role in CoMn-LDH/CC;
图3为实施例1、4的线性循环曲线图和双电层电容图，从图中可以看出含N的催化剂比不含N的催化剂在电解水析氧中的表现更加优异；Figure 3 is the linear cycle curve and double-layer capacitance diagram of Examples 1 and 4. It can be seen from the figure that the N-containing catalyst performs better in the electrolysis of water for oxygen evolution than the N-free catalyst;
图4为实施例1、5、6、7的的线性循环曲线图和过电位图，从图中可以看出最佳的氮掺杂时间为30s；Figure 4 shows the linear cycle curves and overpotential diagrams of Examples 1, 5, 6 and 7. It can be seen from the figure that the optimal nitrogen doping time is 30s;
图5为实施例1、5、6、7的双电层电容图，从图中可以进一步看出氮掺杂时间为30s的催化性能最高。Figure 5 is a double-layer capacitance diagram of Examples 1, 5, 6, and 7. From the figure, it can be further seen that the catalytic performance of the nitrogen doping time of 30 seconds is the highest.
以上所揭露的仅为本发明较佳实施例而已，当然不能以此来限定本发明之权利范围，因此依本发明权利要求所作的等同变化，仍属本发明所涵盖的范围。What is disclosed above is only the preferred embodiment of the present invention. Of course, it cannot be used to limit the scope of the present invention. Therefore, equivalent changes made according to the claims of the present invention still fall within the scope of the present invention.
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| CN202310812561.0ACN117019191A (en) | 2023-07-04 | 2023-07-04 | Efficient electrolyzed water catalyst constructed by atomic doping strategy and preparation method and application thereof |
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