技术领域Technical Field
本发明涉及材料和能源催化技术领域，尤其涉及一种电解天然海水制氢阳极及其制备方法和应用。The present invention relates to the technical field of material and energy catalysis, and in particular to an anode for producing hydrogen by electrolyzing natural seawater, and a preparation method and application thereof.
背景技术Background technique
随着社会经济的快速发展和人类生活水平的不断提高，全球对能源的需求不断增长。随着能源危机和环境污染的日益严重，开发新型可再生能源迫在眉睫。氢被认为是未来一种清洁和理想的燃料，它的氧化产物是水，不含碳。此外，氢燃料的燃烧焓高于其他任何化学燃料。虽然氢燃料的生产备受关注，但可持续生产氢仍然是一个巨大的挑战。With the rapid development of social economy and the continuous improvement of human living standards, the global demand for energy is growing. With the increasing severity of energy crisis and environmental pollution, the development of new renewable energy is urgent. Hydrogen is considered to be a clean and ideal fuel in the future. Its oxidation product is water and it does not contain carbon. In addition, the combustion enthalpy of hydrogen fuel is higher than any other chemical fuel. Although the production of hydrogen fuel has attracted much attention, the sustainable production of hydrogen remains a huge challenge.
电解水制氧是一种高效、清洁和低成本的制氧技术。传统上，贵金属基的电催化剂如Pt,Ir和Ru用于OER。虽然这些贵金属可以提供令人满意的催化效率，但它们是稀缺和昂贵的。这些局限性阻碍了贵金属基催化剂在水裂解方面的实际和大规模应用。目前，大多数OER电催化剂在强酸性或碱性介质中都能有效工作。这些恶劣的环境限制了电极的选择。在中性介质中进行电解作业，可以有效地防止电解液对电解设备的腐蚀。Oxygen production by water electrolysis is an efficient, clean and low-cost oxygen production technology. Traditionally, noble metal-based electrocatalysts such as Pt, Ir and Ru are used for OER. Although these noble metals can provide satisfactory catalytic efficiency, they are scarce and expensive. These limitations hinder the practical and large-scale application of noble metal-based catalysts in water splitting. Currently, most OER electrocatalysts can work effectively in strongly acidic or alkaline media. These harsh environments limit the choice of electrodes. Performing electrolysis in a neutral medium can effectively prevent the corrosion of the electrolyte to the electrolysis equipment.
然而，在中性含氯离子溶液和天然海水条件下，氯离子氧化为氯气为二电子反应、氧气析出为四电子反应，所以氯气析出在动力学上比氧气析出反应更有优势。而氯气是一种有害气体且溶于水会产生氧化性极强的次氯酸根进而损坏设备。因此中性电解海水制氢阳极对氧气析出的选择性是目前面临的重大问题。However, under the conditions of neutral chloride-containing solution and natural seawater, the oxidation of chloride ions to chlorine is a two-electron reaction, and the evolution of oxygen is a four-electron reaction, so the evolution of chlorine is more advantageous than the evolution of oxygen in terms of kinetics. Chlorine is a harmful gas and will produce highly oxidizing hypochlorite ions when dissolved in water, thus damaging the equipment. Therefore, the selectivity of the anode for oxygen evolution in neutral seawater electrolysis hydrogen production is a major problem currently faced.
现有技术中，已经开发了一系列中性溶液中的OER催化剂，包括金属氧化物、磷化物等。例如中国发明专利CN 114774965A公开的电解制氢阳极的改性方法、电解制氢阳极及应用，阳极基体的活性表面上沉积多个银纳米颗粒，形成银纳米层，且所述银纳米颗粒之间存在间隙，部分所述活性表面从所述间隙中暴露，制备的Ag@Na|MnO2/NF作为工作电极，以铂片作为对电极，在高浓度模拟海水为电解质溶液中依旧具有较好的稳定性，其中高浓度模拟海水包括称取40g氢氧化纳和29.22g氯化钠固体溶解于1L的去离子水中配制1MNaOH和0.5MNaCl的溶液。但是，该专利技术在中性海水电解中依旧没有达到很好的选择性。In the prior art, a series of OER catalysts in neutral solutions have been developed, including metal oxides, phosphides, etc. For example, the modification method of the electrolytic hydrogen production anode, the electrolytic hydrogen production anode and its application disclosed in the Chinese invention patent CN 114774965A, a plurality of silver nanoparticles are deposited on the active surface of the anode substrate to form a silver nanolayer, and there are gaps between the silver nanoparticles, and part of the active surface is exposed from the gaps. The prepared Ag@Na|MnO2 /NF is used as the working electrode and the platinum sheet is used as the counter electrode. It still has good stability in the high-concentration simulated seawater as the electrolyte solution, wherein the high-concentration simulated seawater includes weighing 40g of sodium hydroxide and 29.22g of sodium chloride solid and dissolving them in 1L of deionized water to prepare a solution of 1MNaOH and 0.5MNaCl. However, this patented technology still does not achieve good selectivity in neutral seawater electrolysis.
基于现有技术存在的技术问题，本发明提供了一种具有高效、高选择性的电解中性海水制氧催化剂作为阳极，能够实现在中性海水的高效制氢工作。Based on the technical problems existing in the prior art, the present invention provides a highly efficient and highly selective catalyst for electrolyzing neutral seawater to produce oxygen as an anode, which can realize efficient hydrogen production in neutral seawater.
发明内容Summary of the invention
有鉴于此，本发明的目的在于提供一种电解天然海水制氢阳极及其制备方法和应用，能够实现在中性海水的高效制氢工作，具有高效、高选择性电解天然海水制氢阳极，依次包括In view of this, the purpose of the present invention is to provide an anode for hydrogen production by electrolysis of natural seawater and a preparation method and application thereof, which can realize efficient hydrogen production in neutral seawater, and has an efficient and highly selective anode for hydrogen production by electrolysis of natural seawater, which comprises
-导电基底；- an electrically conductive substrate;
-催化层；所述催化层覆设于所述导电基底的表面形成阳极基体；- a catalytic layer; the catalytic layer is coated on the surface of the conductive substrate to form an anode matrix;
-排氯层；所述排氯层为覆盖在所述阳极基体的表面的银纳米颗粒形成制氢阳极；- a chlorine-exhausting layer; the chlorine-exhausting layer is a hydrogen-producing anode formed by silver nanoparticles covering the surface of the anode substrate;
其中，所述银纳米层包括多个银纳米颗粒，且所述银纳米颗粒分布均匀，部分所述催化层从所述颗粒间隙中暴露；所述催化层通过原位生长法将催化剂覆设于所述导电基底的表面形成阳极基体；所述催化剂为氮掺杂的四氧化三钴。The silver nanolayer comprises a plurality of silver nanoparticles, and the silver nanoparticles are evenly distributed, and part of the catalytic layer is exposed from the gaps between the particles; the catalytic layer is formed by coating the catalyst on the surface of the conductive substrate through an in-situ growth method to form an anode matrix; the catalyst is nitrogen-doped cobalt tetroxide.
优选地，所述制氢阳极依次经过在所述导电基底(TM)经电镀-氨气退火在所述导电基底的表面原位生长一层所述催化层形成所述阳极基体(N-Co3O4/TM)，在所述催化层表面沉积一层银具有颗粒间隙的纳米颗粒作为所述排氯层形成所述制氢阳极(Ag@N-Co3O4/TM)。Preferably, the hydrogen-producing anode is sequentially subjected to electroplating-ammonia annealing on the conductive substrate (TM) to in-situ grow a layer of the catalytic layer on the surface of the conductive substrate to form the anode substrate (N-Co3 O4 /TM), and a layer of silver nanoparticles with intergranular spaces is deposited on the surface of the catalytic layer as the chlorine-removing layer to form the hydrogen-producing anode (Ag@N-Co3 O4 /TM).
优选地，所述催化层通过电镀法使钴盐在所述阳极基体的表面进行原位生长，再经过氨气退火后再所述阳极基体表面形成具有致密结构的、片状的催化剂，形成所述催化层。Preferably, the catalytic layer is formed by in-situ growth of cobalt salt on the surface of the anode substrate by electroplating, and then forming a flaky catalyst with a dense structure on the surface of the anode substrate after ammonia annealing to form the catalytic layer.
优选地，所述催化层的厚度为100～300nm。Preferably, the thickness of the catalytic layer is 100-300 nm.
优选地，所述银纳米颗粒的粒径为20～50nm。Preferably, the particle size of the silver nanoparticles is 20 to 50 nm.
优选地，所述排氯层的厚度为5～20nm。Preferably, the thickness of the chlorine-removing layer is 5 to 20 nm.
优选地，所述间隙的大小为100～300nm，所述银纳米层中银纳米颗粒的面密度为50～100/μm2。Preferably, the size of the gap is 100-300 nm, and the surface density of the silver nanoparticles in the silver nanolayer is 50-100/μm2 .
优选地，所述阳极基体包括氢氧化物、氧化物以及磷化物中的任意一种或两种以上的组合。Preferably, the anode matrix includes any one or a combination of two or more of hydroxide, oxide and phosphide.
将所述制氢阳极(Ag@N-Co3O4/TM)作为工作电极，以铂片作为对电极，以0.5M NaCl的模拟天然海水溶液作为电解质溶液中，析氧选择性≥85％。The hydrogen production anode (Ag@N-Co3 O4 /TM) was used as a working electrode, a platinum sheet was used as a counter electrode, and a 0.5M NaCl simulated natural seawater solution was used as an electrolyte solution, and the oxygen evolution selectivity was ≥85%.
为实现另一个目的，本发明还提供了上述制氢阳极的制备方法，所述制氢阳极的制备方法包括在导电基底表面经电镀处理在所述导电基底表面进行原位生长，得到析氧催化剂前驱体(Co(OH)2/TM)；所述析氧催化剂前驱体经氨气退火处理在所述导电基底表面形成催化层作为阳极基体(N-Co3O4/TM)，在所述催化层的表面沉积银纳米颗粒作为排氯层，得到所述制氢阳极(Ag@N-Co3O4/TM)；其中，所述银纳米层包括多个银纳米颗粒，且所述银纳米颗粒分布均匀，所述银纳米颗粒之间具有颗粒间隙能够暴露所述催化层。To achieve another object, the present invention also provides a method for preparing the above-mentioned hydrogen production anode, which comprises the following steps: performing in-situ growth on the surface of a conductive substrate by electroplating treatment to obtain an oxygen evolution catalyst precursor (Co(OH)2 /TM); annealing the oxygen evolution catalyst precursor with ammonia to form a catalytic layer on the surface of the conductive substrate as an anode matrix (N-Co3 O4 /TM), and depositing silver nanoparticles on the surface of the catalytic layer as a chlorine-removing layer to obtain the hydrogen production anode (Ag@N-Co3 O4 /TM); wherein the silver nanolayer comprises a plurality of silver nanoparticles, and the silver nanoparticles are evenly distributed, and there are particle gaps between the silver nanoparticles to expose the catalytic layer.
具体的，包括以下步骤：Specifically, the following steps are included:
S1.将作为导电基底(TM)置于酸液中超声处理，依次分别在混合溶剂中超声清洗，干燥备用；S1. placing the conductive substrate (TM) in an acid solution for ultrasonic treatment, ultrasonically cleaning the substrate in a mixed solvent, and drying the substrate for later use;
S2.将钴盐溶解于去离子水中配制含钴的电镀溶液；S2. dissolving a cobalt salt in deionized water to prepare a cobalt-containing electroplating solution;
S3.将S1得到所述导电基底(TM)浸没入所述电镀溶液中进行电镀处理，在所述阳极基体表面负载有所述析氧催化剂前驱体(Co(OH)2/TM)；S3. Immersing the conductive substrate (TM) obtained in S1 into the electroplating solution for electroplating, and loading the oxygen evolution catalyst precursor (Co(OH)2 /TM) on the surface of the anode substrate;
S4.将S3得到的负载有析氧催化剂前驱体的所述导电基底Co(OH)2/TM)置于在氨气氛围下，经氨气退火处理在所述阳极基体表面形成催化层作为所述阳极基体(N-Co3O4/TM)；所述催化层为负载在所述导电基底表面的氮掺杂的四氧化三钴；S4. placing the conductive substrate Co(OH)2 /TM) loaded with the oxygen evolution catalyst precursor obtained in S3 in an ammonia atmosphere, and forming a catalytic layer on the surface of the anode substrate as the anode substrate (N-Co3 O4 /TM) through ammonia annealing treatment; the catalytic layer is nitrogen-doped cobalt tetroxide loaded on the surface of the conductive substrate;
S5.将S4得到所述阳极基体(N-Co3O4/TM)通过化学沉积的方法，在所述催化层表面形成银纳米层，得到所述制氢阳极(Ag@N-Co3O4/TM)。S5. The anode substrate (N-Co3 O4 /TM) obtained in S4 is subjected to a chemical deposition method to form a silver nanolayer on the surface of the catalyst layer to obtain the hydrogen production anode (Ag@N-Co3 O4 /TM).
优选地，S3中，所述银纳米颗粒的化学沉积方法至少包括采用化学镀法、电镀法或化学氧化还原法中的任意一种；Preferably, in S3, the chemical deposition method of the silver nanoparticles comprises at least one of chemical plating, electroplating or chemical oxidation-reduction method;
优选地，所述化学镀法采用的电镀液包括银盐、络合剂以及还原剂。Preferably, the electroplating solution used in the chemical plating method comprises a silver salt, a complexing agent and a reducing agent.
优选地，所述银盐包括硝酸银。Preferably, the silver salt comprises silver nitrate.
优选地，所述电镀液中银盐的浓度为0.03～0.1mol/L。Preferably, the concentration of the silver salt in the electroplating solution is 0.03-0.1 mol/L.
优选地，所述络合剂包括柠檬酸钠和乙二胺四乙酸二钠中的任意一种或两种的组合。Preferably, the complexing agent includes any one of sodium citrate and disodium edetate or a combination of both.
优选地，所述电镀液中络合剂的浓度为0.06～0.15mol/L。Preferably, the concentration of the complexing agent in the electroplating solution is 0.06-0.15 mol/L.
优选地，所述还原剂包括硼氢化钠和硼氢化锂。Preferably, the reducing agent comprises sodium borohydride and lithium borohydride.
优选地，所述电镀液中还原剂的浓度为0.02～0.05mol/L。Preferably, the concentration of the reducing agent in the electroplating solution is 0.02-0.05 mol/L.
优选地，所述氧化还原镀法采用的化学镀液包括银盐、络合剂以及稳定剂；Preferably, the chemical plating solution used in the redox plating method comprises a silver salt, a complexing agent and a stabilizer;
优选地，所述银盐包括硫酸银、硝酸银中的任意一种或两种的组合。Preferably, the silver salt includes any one of silver sulfate and silver nitrate, or a combination of the two.
优选地，所述络合剂包括焦磷酸钠或焦磷酸钾中的任意一种或两种的组合。Preferably, the complexing agent includes any one of sodium pyrophosphate or potassium pyrophosphate or a combination of the two.
优选地，所述稳定剂包括氨水以及氢氧化钠中的任意一种或两种以上的组合。Preferably, the stabilizer includes any one of ammonia water and sodium hydroxide or a combination of two or more thereof.
优选地，所述银盐的浓度为0.02～0.1mol/L，所述稳定剂的浓度为0.2～0.6mol/L。Preferably, the concentration of the silver salt is 0.02-0.1 mol/L, and the concentration of the stabilizer is 0.2-0.6 mol/L.
优选地，所述氧化还原法镀的温度20～25℃，时间为5～15分钟。Preferably, the oxidation-reduction plating process is carried out at a temperature of 20 to 25° C. and for a time of 5 to 15 minutes.
本发明在现有技术基础上对催化剂进行了改进，使其能够在中性海水中也能够具有良好的析氧选择性。本发明的催化剂在Co3O4的基础上利用氮掺杂技术，提高催化剂的活性，主要地，氮掺杂后Co3O4作为催化剂实现在中性海水中的选择性，其主要作用机理包括：(1)活性位点增多：氮原子的掺杂可以增加催化剂的活性位点数目，提高催化剂的催化活性；(2)电子结构调控：氮原子的掺杂会引起催化剂电子结构的改变，提高催化剂在反应中原子间转移的速率，从而增加反应活性；(3)界面相互作用：氮掺杂可以改善催化剂与反应物之间的相互作用，增强催化剂的稳定性和选择性；(4)表面酸碱性的改变：掺杂氮原子会改变催化剂表面的酸碱性，从而增加催化剂对反应物和中间体的吸附能力，提高反应速率。The present invention improves the catalyst on the basis of the prior art, so that it can also have good oxygen evolution selectivity in neutral seawater. The catalyst of the present invention uses nitrogen doping technology on the basis of Co3 O4 to improve the activity of the catalyst. Mainly, after nitrogen doping, Co3 O4 as a catalyst realizes selectivity in neutral seawater. Its main action mechanism includes: (1) increase in active sites: doping with nitrogen atoms can increase the number of active sites of the catalyst and improve the catalytic activity of the catalyst; (2) electronic structure regulation: doping with nitrogen atoms will cause changes in the electronic structure of the catalyst, increase the rate of atomic transfer of the catalyst in the reaction, thereby increasing the reaction activity; (3) interface interaction: nitrogen doping can improve the interaction between the catalyst and the reactant, and enhance the stability and selectivity of the catalyst; (4) change in surface acidity and alkalinity: doping with nitrogen atoms will change the acidity and alkalinity of the catalyst surface, thereby increasing the adsorption capacity of the catalyst to the reactant and the intermediate, and improving the reaction rate.
通过上述的原理分析可知，通过氮掺杂的Co3O4作为催化层能够进一步增强其在中性海水中的稳定性和反应活性，与现有技术相比较，其不仅能够在中性海水中能够具有更好的析氧选择性，而且其在碱性海水性能也能够实现好的技术效果。From the above principle analysis, it can be seen that using nitrogen-doped Co3 O4 as a catalytic layer can further enhance its stability and reaction activity in neutral seawater. Compared with the existing technology, it not only has better oxygen evolution selectivity in neutral seawater, but also can achieve good technical effects in alkaline seawater.
1.通过采用本发明的技术方案，对催化剂进行氮掺杂，通过氮原子的掺杂来引起催化剂电子结构的改变，提高催化剂在反应中原子间转移的速率，从而增加反应活性，同时可以改善催化剂与反应物之间的相互作用，增强催化剂的稳定性和选择性，最终来实现提高中性海水溶液中的析氧选择性。1. By adopting the technical solution of the present invention, the catalyst is nitrogen-doped, and the doping of nitrogen atoms causes a change in the electronic structure of the catalyst, thereby increasing the rate of atomic transfer of the catalyst in the reaction, thereby increasing the reaction activity, and at the same time improving the interaction between the catalyst and the reactants, enhancing the stability and selectivity of the catalyst, and ultimately achieving the improvement of the oxygen evolution selectivity in the neutral seawater solution.
2.通过采用本发明的技术方案，通过阳极基体表面覆盖银纳米层，在电解天然海水制氢过程中氯离子被吸附到银表面，形成一层排氯层，阻碍溶液中其他氯离子在电极表面的继续吸附，达到延缓氯离子到达电极表面发生氧化反应的作用，并且适当的银纳米层结构不会对阳极基体的催化作用产生较大影响，从而提高海水电解制氢反应中阳极的析氧选择性。2. By adopting the technical solution of the present invention, the surface of the anode substrate is covered with a silver nanolayer, and in the process of electrolyzing natural seawater to produce hydrogen, chloride ions are adsorbed onto the silver surface to form a chlorine-removing layer, which hinders the continued adsorption of other chloride ions in the solution on the electrode surface, thereby delaying the chloride ions from reaching the electrode surface for oxidation reaction, and the appropriate silver nanolayer structure will not have a significant effect on the catalytic effect of the anode substrate, thereby improving the oxygen evolution selectivity of the anode in the seawater electrolysis hydrogen production reaction.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是本发明实施例1提供的电解制氢阳极中阳极基体的X射线衍射图。FIG1 is an X-ray diffraction diagram of an anode substrate in an anode for producing hydrogen by electrolysis provided in Example 1 of the present invention.
图2是本发明实施例1提供的电解制氢阳极中阳极基体的表面形貌电镜照片。FIG. 2 is an electron microscope photograph of the surface morphology of the anode substrate in the electrolytic hydrogen production anode provided in Example 1 of the present invention.
图3是本发明实施例1提供的电解制氢阳极的表面形貌电镜照片。FIG3 is an electron microscope photograph of the surface morphology of the electrolytic hydrogen production anode provided in Example 1 of the present invention.
图4a-图4d分别是本发明实施例1提供的电解制氢阳极中阳极基体的元素分布(EDS)照片。4a-4d are respectively photos of element distribution (EDS) of the anode substrate in the electrolytic hydrogen production anode provided in Example 1 of the present invention.
图5是本发明实施例1提供的电解天然海水制氢阳极的析氧选择性测试图。FIG5 is a test diagram of oxygen evolution selectivity of the anode for producing hydrogen by electrolyzing natural seawater provided in Example 1 of the present invention.
图6是本发明实施例2提供的电解天然海水制氢阳极的析氧选择性测试图。FIG6 is a test diagram of oxygen evolution selectivity of the anode for producing hydrogen by electrolyzing natural seawater provided in Example 2 of the present invention.
具体实施方式Detailed ways
使本发明实施例的目的、技术方案和优点更加清楚，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本发明的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。To make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the protection scope of the present invention.
在下面的描述中阐述了很多具体细节以便于充分理解本发明，但是，本发明还可以采用其他不同于在此描述的方式来实施，因此，本发明的保护范围并不受下面公开的具体实施例的限制。In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Therefore, the protection scope of the present invention is not limited to the specific embodiments disclosed below.
而且，诸如“第一”和“第二”等之类的关系术语仅仅用来将一个与另一个具有相同名称的部件或方法步骤区分开来，而不一定要求或者暗示这些部件或方法步骤之间存在任何这种实际的关系或者顺序。Moreover, relational terms such as “first” and “second” and the like are merely used to distinguish one component or method step from another having the same name, but do not necessarily require or imply any such actual relationship or order between these components or method steps.
本发明提供了一种提高天然海水电解阳极选择性的电极改性方法，为提高海水电解制氢过程中阳极的析氧选择性提供了新思路。The present invention provides an electrode modification method for improving the anode selectivity in natural seawater electrolysis, and provides a new idea for improving the oxygen evolution selectivity of the anode in the process of hydrogen production by seawater electrolysis.
本发明实施例提供一种电解天然海水制氢阳极，包括导电基底、催化层和排氯层；所述催化层覆设于导电基底的表面形成阳性基体；所述排氯层为覆盖在所述催化层的表面的银纳米颗粒；所述银纳米层包括多个银纳米颗粒，且所述银纳米颗粒分布均匀，部分所述催化层从所述颗粒间隙中暴露；所述催化层作为催化剂催化电解制氢，所述催化剂为氮掺杂的四氧化三钴。通过阳极基体表面覆盖银纳米层，在电解天然海水制氢过程中氯离子被吸附到银表面，形成一层排氯层，阻碍溶液中其他氯离子在电极表面的继续吸附，达到延缓氯离子到达电极表面发生氧化反应的作用，并且适当的银纳米层结构不会对阳极基体的催化作用产生较大影响，从而提高海水电解制氢反应中阳极的析氧选择性。The embodiment of the present invention provides an anode for hydrogen production by electrolysis of natural seawater, comprising a conductive substrate, a catalytic layer and a chlorine-removing layer; the catalytic layer is coated on the surface of the conductive substrate to form a positive substrate; the chlorine-removing layer is silver nanoparticles coated on the surface of the catalytic layer; the silver nanolayer comprises a plurality of silver nanoparticles, and the silver nanoparticles are evenly distributed, and part of the catalytic layer is exposed from the gaps between the particles; the catalytic layer acts as a catalyst to catalyze hydrogen electrolysis, and the catalyst is nitrogen-doped cobalt tetraoxide. By covering the surface of the anode substrate with a silver nanolayer, chloride ions are adsorbed onto the silver surface during hydrogen production by electrolysis of natural seawater, forming a chlorine-removing layer, which hinders the continued adsorption of other chloride ions in the solution on the electrode surface, thereby delaying the chloride ions from reaching the electrode surface to undergo oxidation reaction, and the appropriate silver nanolayer structure will not have a significant impact on the catalytic effect of the anode substrate, thereby improving the oxygen evolution selectivity of the anode in the seawater electrolysis hydrogen production reaction.
在电解天然海水制氢过程中，氯离子会优选被吸附到上述银纳米颗粒的表面，进而会形成一层排氯层，阻碍溶液中其他氯离子在电极表面的继续吸附，从而可以达降低阳极表面氯离子浓度的作用，并且，适当的银纳米层结构尤其是上述间隙，使得上述阳极基体的活性表面得以暴露，因此不会对阳极基体本来的催化作用产生较大影响。In the process of electrolyzing natural seawater to produce hydrogen, chloride ions will be preferentially adsorbed onto the surface of the silver nanoparticles, thereby forming a chlorine-repelling layer, which hinders the continued adsorption of other chloride ions in the solution on the electrode surface, thereby achieving the effect of reducing the chloride ion concentration on the anode surface. In addition, the appropriate silver nanolayer structure, especially the above-mentioned gaps, exposes the active surface of the anode substrate, so it will not have a significant impact on the original catalytic effect of the anode substrate.
采用本发明的技术方案，利用对阳极基体进行改性，增强制氢阳极的选择性的同时，能够将其应用于中性海水电解析氧工艺中。By adopting the technical solution of the present invention, the anode substrate is modified to enhance the selectivity of the hydrogen production anode and can be applied to the neutral seawater electrolysis oxygen process.
具体地，改性方法包括将制氢阳极依次经过在所述阳极基体(TM)经电镀-氨气退火在所述阳极基体的表面原位生长一层所述催化层(N-Co3O4/TM)，在催化层表面沉积一层银具有颗粒间隙的纳米颗粒作为排氯层(Ag@N-Co3O4/TM)。Specifically, the modification method includes sequentially subjecting the hydrogen-producing anode to electroplating-ammonia annealing on the anode substrate (TM) to in-situ grow a layer of the catalytic layer (N-Co3 O4 /TM) on the surface of the anode substrate, and depositing a layer of silver nanoparticles with intergranular spaces on the surface of the catalytic layer as a chlorine-removing layer (Ag@N-Co3 O4 /TM).
在一些实施方案中，催化层通过电镀法使钴盐在所述阳极基体的表面进行原位生长，再经过氨气退火后再阳极基体表面生成具有致密结构的、片状的催化剂，形成催化层。In some embodiments, the catalytic layer is formed by in-situ growth of cobalt salt on the surface of the anode substrate by electroplating, and then a densely structured, flaky catalyst is generated on the surface of the anode substrate after ammonia annealing to form a catalytic layer.
据上述方案提供的制氢阳极的制备方案，进一步地，本申请提供一种电解中性天然海水的改性方法，包括如下的步骤：According to the preparation scheme of the hydrogen production anode provided by the above scheme, further, the present application provides a modification method for electrolyzing neutral natural seawater, comprising the following steps:
提供阳极基体，所述阳极基体能够用于催化电解制氢。An anode substrate is provided, which can be used for catalytic electrolysis to produce hydrogen.
在阳极基体表面经过原位生长-氨气退火处理得到一层催化层。A catalyst layer is obtained on the surface of the anode substrate through in-situ growth-ammonia annealing treatment.
在催化层的活性表面上沉积银纳米层，所述银纳米层包括多个银纳米颗粒，且所述银纳米颗粒之间存在间隙，部分所述活性表面从所述间隙中暴露。A silver nanolayer is deposited on the active surface of the catalytic layer. The silver nanolayer includes a plurality of silver nanoparticles. There are gaps between the silver nanoparticles, and a portion of the active surface is exposed from the gaps.
作为一些典型的应用示例，可以采用过渡金属盐溶液作为电镀液，在导电基底上原位电镀致密包覆的催化剂，作为所述的阳极基体，随后再以化学法镀一定量的银，所制备的阳极催化剂具有优异的电催化天然海水析氧性能和选择性。As some typical application examples, a transition metal salt solution can be used as an electroplating solution to in-situ electroplate a densely coated catalyst on a conductive substrate as the anode substrate, and then a certain amount of silver is chemically plated. The prepared anode catalyst has excellent electrocatalytic natural seawater oxygen evolution performance and selectivity.
其中，选择的阳极基体本身具有一定的海水电解析氧活性及选择性，因此，其能够用于催化电解天然海水制氢。Among them, the selected anode matrix itself has a certain seawater electrolysis oxygen decomposition activity and selectivity, so it can be used for catalytic electrolysis of natural seawater to produce hydrogen.
当然，上述技术方案还可以包括制得电解天然海水制氢阳极后，对其进行材料表征和选择性以及稳定性的测试表征的步骤，这些步骤可以是为了质量监控，也可以是为了深入研究，无论是否进行表征以及以何种手段进行表征，均属于本发明的保护范围之内。对改性处理后的阳极进行材料表征可以包括但不限于：X射线衍射(XRD)，确定包覆后材料特性；扫描电子显微镜(SEM)、透射电子显微镜(TEM)对材料形貌、晶格及元素含量进行表征；对改性处理后的阳极进行选择性和稳定性表征，可以包括但不限于：线性扫描伏安法(LSV)和i-t恒电流测试。Of course, the above technical solution may also include the steps of testing and characterizing the material and the selectivity and stability of the anode after the electrolysis of natural seawater for hydrogen production. These steps may be for quality control or for in-depth research. Whether or not the characterization is performed and by what means, they all fall within the scope of protection of the present invention. The material characterization of the modified anode may include, but is not limited to: X-ray diffraction (XRD) to determine the material properties after coating; scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to characterize the material morphology, lattice and element content; the selectivity and stability of the modified anode may include, but is not limited to: linear sweep voltammetry (LSV) and i-t constant current test.
在一些实施方案中，排氯层(银纳米层)优选为均匀分布的银纳米颗粒，其粒径优选可以为10-30nm。In some embodiments, the chlorine-repelling layer (silver nanolayer) is preferably uniformly distributed silver nanoparticles, and the particle size thereof may preferably be 10-30 nm.
在一些实施方案中，所述间隙的大小可选范围为100-300nm，优选可以为300nm左右，所述银纳米层中银纳米颗粒的面密度的可选范围为100-300/μm2，优选可以为150/μm2左右。In some embodiments, the size of the gap may be in the range of 100-300 nm, preferably about 300 nm, and the surface density of the silver nanoparticles in the silver nanolayer may be in the range of 100-300/μm2, preferably about 150/μm2.
发明人发现，上述银纳米层的形貌、粒径、间隙大小及间隙率等特点是有效排氯并对催化效率不产生较大负面影响的较为关键的特征。想要形成这种特征，需要对沉积上述银纳米层的工艺参数进行独特的设计，以形成上述特殊的形貌，例如在电镀沉积时，其镀液浓度和电镀电流和时间等，或在化学还原镀时，其镀液浓度、搅拌速率等参数。只有设置合适的沉积过程，才可以形成上述较为特殊的银纳米层形貌。The inventors have found that the morphology, particle size, gap size and gap ratio of the above-mentioned silver nanolayer are the key features for effectively removing chlorine without having a significant negative impact on the catalytic efficiency. In order to form such features, it is necessary to uniquely design the process parameters for depositing the above-mentioned silver nanolayer to form the above-mentioned special morphology, such as the concentration of the plating solution, the plating current and time during electroplating deposition, or the concentration of the plating solution, the stirring rate and other parameters during chemical reduction plating. Only by setting a suitable deposition process can the above-mentioned relatively special silver nanolayer morphology be formed.
在一些实施方案中，所述阳极基体包括氢氧化物、氧化物、氮化物以及磷化物中的任意一种或两种以上的组合。可以是单纯由上述材料构成的电极，也可以是上述材料或其组合与其他材料复合组成的复合电极，例如与导电剂复合、表面复合氮化层或其他镀层，或与成型基材复合成特定形状等。In some embodiments, the anode substrate includes any one or a combination of two or more of hydroxides, oxides, nitrides and phosphides. It can be an electrode composed solely of the above materials, or a composite electrode composed of the above materials or their combination and other materials, such as a composite electrode with a conductive agent, a composite nitride layer or other coating on the surface, or a composite electrode with a molded substrate into a specific shape.
在一些实施方案中，包括：至少采用电镀法、化学镀法以及氧化还原法中的任意一种方法在所述阳极基体的活性表面上沉积多个银纳米颗粒。沉积的方法可以根据上述阳极基体的特点进行选择，例如电镀法包覆银不会影响步骤(1)中的阳极催化剂本征性质，适应于各类阳极电极。电镀法包覆银的方法包括将电极材料置于电解液中，通电，将溶液中的银离子还原到电极表面。化学镀法包覆银适用于氮化物等不易于被还原剂还原或破坏原有结构的材料，步骤包括：电极预处理、镀液的配置，化学挂镀装置的搭建以及化学镀装置的设定和电镀完成电极的后处理，适用于氮化物等不易于被还原剂还原或破坏原有结构的材料，能使银均匀牢固的生长在电极的表面。氧化还原法包覆银适能够大面积、快速、均匀对阳极进行银包覆，但氧化还原镀时一般只适用于可以发生氧化还原的氢氧化物，步骤包括：电极预处理、氧化还原镀装置的搭建以及电极的后处理。In some embodiments, it includes: at least one of electroplating, chemical plating and redox method is used to deposit a plurality of silver nanoparticles on the active surface of the anode substrate. The deposition method can be selected according to the characteristics of the anode substrate. For example, the silver coating by electroplating will not affect the intrinsic properties of the anode catalyst in step (1), and is suitable for various types of anode electrodes. The method of coating silver by electroplating includes placing the electrode material in an electrolyte, applying electricity, and reducing the silver ions in the solution to the electrode surface. The chemical plating method is suitable for materials such as nitrides that are not easily reduced by reducing agents or have their original structures destroyed. The steps include: electrode pretreatment, configuration of the plating solution, construction of a chemical plating device, setting of a chemical plating device, and post-treatment of the electrode after electroplating. It is suitable for materials such as nitrides that are not easily reduced by reducing agents or have their original structures destroyed, and can make silver grow evenly and firmly on the surface of the electrode. The redox method of coating silver is suitable for large-scale, fast, and uniform silver coating of the anode, but redox plating is generally only suitable for hydroxides that can undergo redox. The steps include: electrode pretreatment, construction of a redox plating device, and post-treatment of the electrode.
在一些实施方案中，所述电镀法的电镀液包括银盐、络合剂以及碱性物质。In some embodiments, the plating solution of the electroplating method includes a silver salt, a complexing agent, and an alkaline substance.
在一些实施方案中，所述银盐包括硝酸银。In some embodiments, the silver salt comprises silver nitrate.
在一些实施方案中，所述电镀液中银盐的浓度为0.01-0.06mol/L。In some embodiments, the concentration of the silver salt in the electroplating solution is 0.01-0.06 mol/L.
在一些实施方案中，所述络合剂包括焦磷酸钠或焦磷酸钾中的任意一种或两种的组合。In some embodiments, the complexing agent includes either sodium pyrophosphate or potassium pyrophosphate or a combination of both.
在一些实施方案中，所述电镀液中络合剂的浓度为0.06-0.15mol/L。In some embodiments, the concentration of the complexing agent in the electroplating solution is 0.06-0.15 mol/L.
在一些实施方案中，所述碱性物质包括氢氧化钠或氢氧化钾。In some embodiments, the alkaline substance comprises sodium hydroxide or potassium hydroxide.
在一些实施方案中，所述电镀液中碱性物质的浓度为0.2-1.0mol/L。In some embodiments, the concentration of the alkaline substance in the electroplating solution is 0.2-1.0 mol/L.
在一些实施方案中，所述电镀法采用的电流密度为3-10mA/cm2。In some embodiments, the electroplating method uses a current density of 3-10 mA/cm2 .
在一些实施方案中，所述电镀法为恒电流模式。In some embodiments, the electroplating method is in constant current mode.
在一些实施方案中，所述电镀法的时间为5～15min。In some embodiments, the electroplating process lasts for 5 to 15 minutes.
可以看出，上述优选的电镀方式是区别于传统的电镀银的，其银盐浓度、电流密度以及电镀时间等均与传统的电镀银不同，这是为形成上述特殊的银纳米层结构而进行的改变。It can be seen that the above preferred electroplating method is different from the traditional silver electroplating. Its silver salt concentration, current density and electroplating time are different from those of the traditional silver electroplating. This is a change made to form the above special silver nanolayer structure.
在一些实施方案中，所述化学镀法采用的化学镀液包括银盐、还原剂以及络合剂。In some embodiments, the chemical plating solution used in the chemical plating method includes a silver salt, a reducing agent, and a complexing agent.
在一些实施方案中，所述银盐包括硫酸银、硝酸银或两者的组合，但不限于此，其他常见的化学镀银所用银盐亦可，所述还原剂包括葡萄糖、硼氢化钠或两者的组合，也应不仅限于此，所述络合剂包括柠檬酸钠、乙二胺四乙酸二钠或其中两者及以上的组合，亦不应仅限于此。In some embodiments, the silver salt includes silver sulfate, silver nitrate, or a combination of the two, but is not limited thereto. Other common silver salts used for chemical silver plating may also be used. The reducing agent includes glucose, sodium borohydride, or a combination of the two, but should not be limited thereto. The chelating agent includes sodium citrate, disodium ethylenediaminetetraacetate, or a combination of two or more thereof, but should not be limited thereto.
应用怎样的化学镀试剂并非本案所发明的核心内容，本案的核心在于利用无论是电镀还是化学镀和氧化还原镀，通过控制反应条件，来实现上述特定的银纳米层结构，进而实现阳极的保护。The application of chemical plating reagents is not the core content of the invention of this case. The core of this case is to use electroplating, chemical plating and redox plating to control the reaction conditions to achieve the above-mentioned specific silver nanolayer structure and thus achieve anode protection.
在一些实施方案中，所述银盐的浓度为0.03-0.1mol/L，所述还原剂的浓度为0.02-0.5mol/L，所述络合剂的浓度为0.06-0.15mol/L。In some embodiments, the concentration of the silver salt is 0.03-0.1 mol/L, the concentration of the reducing agent is 0.02-0.5 mol/L, and the concentration of the complexing agent is 0.06-0.15 mol/L.
在一些实施方案中，化学镀温度20-25℃，时间5-15分钟。In some embodiments, the electroless plating temperature is 20-25° C. and the time is 5-15 minutes.
在一些实施方案中，所述氧化还原镀以置换反应的方式进行。In some embodiments, the redox plating is performed as a displacement reaction.
在一些实施方案中，所述银盐为硝酸银、硫酸银或两者的组合，反应时间为1-5min。In some embodiments, the silver salt is silver nitrate, silver sulfate, or a combination of the two, and the reaction time is 1-5 min.
在氧化还原镀银中，其时间应严格控制，以实现上述的银纳米层的独特结构。In the redox silver plating, the time should be strictly controlled to achieve the unique structure of the silver nanolayer mentioned above.
参见图1-图6，本发明实施例还提供一种电解天然海水制氢阳极，所述电解制氢阳极包括阳极基体以及覆设于所述阳极基体催化剂上的银纳米层；所述阳极基体本身能够用于电解制氢，所述银纳米层包括多个银纳米颗粒，且所述银纳米颗粒之间存在间隙，部分所述活性表面从所述间隙中暴露。Referring to Figures 1 to 6, an embodiment of the present invention further provides an anode for producing hydrogen by electrolysis of natural seawater, wherein the anode comprises an anode substrate and a silver nanolayer coated on the anode substrate catalyst; the anode substrate itself can be used for hydrogen electrolysis, the silver nanolayer comprises a plurality of silver nanoparticles, and there are gaps between the silver nanoparticles, and part of the active surface is exposed from the gaps.
在一些实施方案中，所述银纳米层的厚度为5-20nm。In some embodiments, the silver nanolayer has a thickness of 5-20 nm.
上述电解天然海水制氢阳极可以由上文所提供的的改性方法制得，也可以由其他方法制得，只要是具备同样的结构特征亦均应属于本发明的保护范围，其也可以具备如上文所述的银纳米层同样的形貌、尺寸间隙等特征。The above-mentioned anode for hydrogen production by electrolysis of natural seawater can be prepared by the modification method provided above, or by other methods. As long as it has the same structural characteristics, it should also fall within the protection scope of the present invention. It can also have the same morphology, size gap and other characteristics as the silver nanolayer described above.
本发明实施例还提供上述电解天然海水制氢阳极在含氯离子水溶液电解制氢中的应用，当然，出于成本考虑，所述的含氯离子水溶液的最优选择为天然海水，但也并非限于此，例如，工业含氯废水，或特别配置的氯化钠或氯化钾水溶液亦属于本案的保护范围。下面结合实施例和附图说明对本发明内容进行进一步的解释说明，所涉及的提升电解天然海水制氢阳极析氧选择性的改性方法、电解海水制氢阳极以及应用，本发明所涉及的实施例不限于此。The embodiment of the present invention also provides the application of the above-mentioned electrolysis of natural seawater hydrogen production anode in the electrolysis of chloride ion aqueous solution hydrogen production. Of course, for cost considerations, the optimal choice of the chloride ion aqueous solution is natural seawater, but it is not limited to this. For example, industrial chlorine-containing wastewater, or specially configured sodium chloride or potassium chloride aqueous solution also belong to the protection scope of this case. The following is a further explanation of the content of the present invention in conjunction with the embodiments and the accompanying drawings. The modification method for improving the oxygen evolution selectivity of the electrolysis of natural seawater hydrogen production anode, the electrolysis of seawater hydrogen production anode and its application are involved, and the embodiments involved in the present invention are not limited to this.
实施例1Example 1
本实施例提供一种高稳定性、高选择性的制氢阳极，具体制备步骤包括：This embodiment provides a highly stable and highly selective hydrogen production anode, and the specific preparation steps include:
(1)将商用钛网(TM)(作为导电基底)裁成1cm×3cm的长条状，在2mol·L-1的盐酸溶液中超声处理3min，然后依次分别在去离子水和无水乙醇中超声清洗三次，空气中自然干燥备用。(1) A commercial titanium mesh (TM) (as a conductive substrate) was cut into strips of 1 cm × 3 cm, ultrasonically treated in a 2 mol·L-1 hydrochloric acid solution for 3 min, and then ultrasonically cleaned three times in deionized water and anhydrous ethanol, respectively, and dried naturally in air for later use.
(2)称取5.14g六水合硝酸钴溶解于1L去离子水中配制含钴的电镀溶液，取130mL并将其转移到200mL的电镀池中。(2) Weigh 5.14 g of cobalt nitrate hexahydrate and dissolve it in 1 L of deionized water to prepare a cobalt-containing electroplating solution. Take 130 mL and transfer it to a 200 mL electroplating bath.
(3)将清洗后的钛网浸没入反应溶液，以-1V的电压电镀10min得到高稳定性的Co(OH)2/TM高稳定性析氧催化剂作为电解的阳极，随后在氨气气氛下350℃退火得到N-Co3O4/TM，最后将上述阳极基体置于化学镀银溶液中在一定的旋转搅拌下浸泡10min，200rpm的下镀银10min为本实施例选择的优选镀银条件。(3) The cleaned titanium mesh was immersed in the reaction solution, and electroplated at a voltage of -1 V for 10 min to obtain a high-stability Co(OH)2 /TM high-stability oxygen evolution catalyst as the anode of electrolysis, followed by annealing at 350°C in an ammonia atmosphere to obtain N-Co3 O4 /TM. Finally, the above-mentioned anode substrate was placed in a chemical silver plating solution and immersed for 10 min under certain rotation and stirring. Silver plating at 200 rpm for 10 min is the preferred silver plating condition selected in this embodiment.
(4)称取29.22g氯化钠固体溶解于1L的去离子水中配制0.5MNaCl模拟中性天然海水溶液作为电解质溶液备用。(4) Weigh 29.22 g of sodium chloride solid and dissolve it in 1 L of deionized water to prepare a 0.5 M NaCl simulated neutral natural seawater solution as an electrolyte solution for later use.
(5)将步骤(3)Ag@N-Co3O4/TM作为工作电极，以铂片作为对电极，以步骤(4)中的模拟天然海水为电解质，分别在20、40、60、80、100mAcm-2的电流密度下进行选择性测试。(5) Using the Ag@N-Co3 O4 /TM prepared in step (3) as the working electrode, the platinum sheet as the counter electrode, and the simulated natural seawater prepared in step (4) as the electrolyte, selectivity tests were performed at current densities of 20, 40, 60, 80, and 100 mAcm -2 , respectively.
形貌和性能表征：Morphology and performance characterization:
如图1所示，为N-Co3O4/TM阳极的X射线衍射图谱，可以看到所合成的N-Co3O4的晶相对应于Co3O4的标准衍射峰，说明N是以掺杂的形式进入而不是形成其他新相，说明氮掺杂成功。As shown in Figure 1, which is the X-ray diffraction pattern of the N-Co3 O4 /TM anode, it can be seen that the crystal phase of the synthesized N-Co3 O4 corresponds to the standard diffraction peak of Co3 O4 , indicating that N enters in the form of doping rather than forming other new phases, indicating that nitrogen doping is successful.
如图2所示，为N-Co3O4/TM阳极的表面形貌，图中可以看到N-Co3O4纳米片的形状一致且大小、薄厚均匀，厚度约200nm，N-Co3O4形成的催化层形貌良好。As shown in Figure 2, it is the surface morphology of the N-Co3 O4 /TM anode. It can be seen in the figure that the N-Co3 O4 nanosheets have consistent shapes and uniform sizes and thicknesses, with a thickness of about 200nm. The catalytic layer formed by N-Co3 O4 has good morphology.
如图3所示，为Ag@N-Co3O4/TM的SEM图，图中可以看到在颜色较浅的片状催化剂结构上分布有颜色较深的分散的点状银颗粒，粒径约为20～50nm，可以直接推测得到纳米银颗粒均匀分布在N-Co3O4/TM阳极的表面。As shown in Figure 3, it is a SEM image of Ag@N-Co3 O4 /TM. In the image, it can be seen that darker colored dispersed dot-shaped silver particles are distributed on the lighter colored flake catalyst structure, and the particle size is about 20 to 50 nm. It can be directly inferred that the nano-silver particles are uniformly distributed on the surface of the N-Co3 O4 /TM anode.
如图4所示，为N-Co3O4/TM阳极的元素分布图片，其中氮元素和氧元素均匀分布，证明氮元素均匀的掺杂到了催化剂中。As shown in FIG. 4 , it is an element distribution picture of the N-Co3 O4 /TM anode, in which nitrogen and oxygen elements are evenly distributed, proving that nitrogen is evenly doped into the catalyst.
参阅图5，为步骤(5)的测试结果，在多个电流密度下电解中性天然海水的析氧选择性达到90％，相比于N-Co3O4/TM选择性提升近40％。Referring to FIG. 5 , which is the test result of step (5), the oxygen evolution selectivity of electrolyzing neutral natural seawater at multiple current densities reaches 90%, which is nearly 40% higher than that of N-Co3 O4 /TM.
实施例2Example 2
本实施例提供一种高稳定性、高选择性的制氢阳极，具体制备步骤包括：This embodiment provides a highly stable and highly selective hydrogen production anode, and the specific preparation steps include:
(1)将商用钛网裁成1cm×3cm的长条状，在2mol·L-1的盐酸溶液中超声处理3min，然后依次分别在去离子水和无水乙醇中超声清洗三次，空气中自然干燥备用，按照实施例1相同的方法制得阳极基体N-Co3O4/TM。(1) A commercial titanium mesh was cut into strips of 1 cm × 3 cm, ultrasonically treated in a 2 mol·L-1 hydrochloric acid solution for 3 min, then ultrasonically cleaned three times in deionized water and anhydrous ethanol respectively, and dried naturally in air for later use. The anode substrate N-Co3 O4 /TM was prepared in the same manner as in Example 1.
(2)称取10gNaOH、22.5g丁二酰亚胺、22.5g焦磷酸钠、2.5g硝酸银，溶于500mL去离子水中配置镀银电镀液。(2) Weigh 10 g of NaOH, 22.5 g of succinimide, 22.5 g of sodium pyrophosphate, and 2.5 g of silver nitrate, and dissolve them in 500 mL of deionized water to prepare a silver plating solution.
(3)将烘干后的N-Co3O4/TM电极片置于(2)配置好的电镀液中进行电镀，优选镀银条件为5mAcm-2电流密度下电镀5min，得到高选择性的Ag@N-Co3O4/TM析氧阳极，其银颗粒的大小由电镀时间决定，银颗粒的生长速度由电流密度的大小控制。(3) Placing the dried N-Co3 O4 /TM electrode sheet in the electroplating solution prepared in (2) for electroplating. The preferred silver plating condition is electroplating for 5 min at a current density of 5 mA cm-2 to obtain a highly selective Ag@N-Co3 O4 /TM oxygen evolution anode. The size of the silver particles is determined by the electroplating time, and the growth rate of the silver particles is controlled by the current density.
(4)称取29.22g氯化钠固体溶解于1L的去离子水中配制0.5M NaCl模拟中性天然海水溶液作为电解质溶液备用。(4) Weigh 29.22 g of sodium chloride solid and dissolve it in 1 L of deionized water to prepare a 0.5 M NaCl simulated neutral natural seawater solution as an electrolyte solution for later use.
(5)将步骤(3)中制备的Ag@N-Co3O4/TM作为工作电极，以铂片作为对电极，以步骤(4)中的模拟天然海水为电解质，在20、40、60、80、100mA/cm2的电流密度下测试Ag@N-Co3O4/TM的选择性。(5) The Ag@N-Co3 O4 /TM prepared in step (3) was used as the working electrode, the platinum sheet was used as the counter electrode, and the simulated natural seawater in step (4) was used as the electrolyte. The selectivity of Ag@N-Co3 O4 /TM was tested at current densities of 20, 40, 60, 80, and 100 mA/cm2 .
如图6所示，本实施例制备的电极在电解模拟天然海水中的选择性达85％，说明此方法制备的Ag@N-Co3O4/TM阳极，起到了提升电解中性天然海水析氧选择性的作用。As shown in FIG6 , the selectivity of the electrode prepared in this example in the electrolysis of simulated natural seawater is 85%, indicating that the Ag@N-Co3 O4 /TM anode prepared by this method plays a role in improving the selectivity of oxygen evolution in the electrolysis of neutral natural seawater.
实施例3Example 3
本实施例提供一种高稳定性、高选择性的制氢阳极，具体制备步骤包括：This embodiment provides a highly stable and highly selective hydrogen production anode, and the specific preparation steps include:
(1)将商用钛网裁成1cm×3cm的长条状，在2mol·L-1的盐酸溶液中超声处理3min，然后依次分别在去离子水和无水乙醇中超声清洗三次，空气中自然干燥备用，按照实施例1相同的方法制得阳极基体Co(OH)2/TM。(1) A commercial titanium mesh was cut into strips of 1 cm × 3 cm, ultrasonically treated in a 2 mol·L-1 hydrochloric acid solution for 3 min, then ultrasonically cleaned three times in deionized water and anhydrous ethanol respectively, and dried naturally in air for later use. The anode substrate Co(OH)2 /TM was prepared in the same manner as in Example 1.
(2)称取8.5g硝酸银1L去离子水中配制含银离子溶液，并将其转移到50mL挂镀池中置于暗处。(2) Weigh 8.5 g of silver nitrate into 1 L of deionized water to prepare a silver ion solution, and transfer it to a 50 mL rack plating tank and place it in a dark place.
(3)将烘干后的Co(OH)2/TM电极片置于(2)配置好的反应液中进行反应，于暗处悬挂浸泡5min后取出得到电解天然海水高选择性析氧阳极Ag@Co(OH)2/TM。(3) The dried Co(OH)2 /TM electrode sheet was placed in the reaction solution prepared in (2) for reaction, and was suspended and soaked in the dark for 5 minutes before being taken out to obtain the highly selective oxygen evolution anode Ag@Co(OH)2 /TM for electrolysis of natural seawater.
(4)称取29.22g氯化钠固体溶解于1L的去离子水中配制0.5M NaCl模拟中性天然海水溶液作为电解质溶液备用。(4) Weigh 29.22 g of sodium chloride solid and dissolve it in 1 L of deionized water to prepare a 0.5 M NaCl simulated neutral natural seawater solution as an electrolyte solution for later use.
(5)将步骤(3)中制备的Ag@Co(OH)2/TM作为工作电极，以铂片作为对电极，以步骤(4)中的高浓度模拟海水为电解质，在20、40、60、80、100mA/cm2的电流密度下测试Ag@Co(OH)2/TM的选择性以及稳定性。(5) The Ag@Co(OH)2 /TM prepared in step (3) was used as the working electrode, the platinum sheet was used as the counter electrode, and the high concentration simulated seawater in step (4) was used as the electrolyte. The selectivity and stability of the Ag@Co(OH)2 /TM were tested at current densities of 20, 40, 60, 80, and 100 mA/cm2 .
采用本实施例提供的技术方案制备的电极在模拟天然海水中电解的稳定性近300小时，选择性达85％，说明此方法制备的Ag@Co(OH)2/TM阳极，起到了提升电解中性天然海水析氧选择性的作用。The electrode prepared by the technical solution provided in this embodiment has a stability of nearly 300 hours in the electrolysis of simulated natural seawater, and a selectivity of 85%, indicating that the Ag@Co(OH)2 /TM anode prepared by this method plays a role in improving the selectivity of oxygen evolution in the electrolysis of neutral natural seawater.
对比例1Comparative Example 1
本对比例提供一种制氢阳极，具体制备步骤包括：This comparative example provides a hydrogen production anode, and the specific preparation steps include:
(1)将商用钛网裁成1cm×3cm的长条状，在2mol·L-1的盐酸溶液中超声处理3min，然后依次分别在去离子水和无水乙醇中超声清洗三次，空气中自然干燥备用，按照实施例1相同的方法制得阳极基体N-Co3O4/TM。(1) A commercial titanium mesh was cut into strips of 1 cm × 3 cm, ultrasonically treated in a 2 mol·L-1 hydrochloric acid solution for 3 min, then ultrasonically cleaned three times in deionized water and anhydrous ethanol respectively, and dried naturally in air for later use. The anode substrate N-Co3 O4 /TM was prepared in the same manner as in Example 1.
(2)称取29.22g氯化钠固体溶解于1L的去离子水中配制0.5M NaCl模拟天然海水溶液作为电解质溶液备用。(2) Weigh 29.22 g of sodium chloride solid and dissolve it in 1 L of deionized water to prepare a 0.5 M NaCl simulated natural seawater solution as an electrolyte solution for later use.
(3)将步骤(1)中制备的N-Co3O4/TM作为工作电极，以铂片作为对电极，以实施例1中的步骤(4)中的模拟中性天然海水为电解质，在20、40、60、80、100mA/cm2的电流密度下测试N-Co3O4/TM的选择性，采用本对比例提供的技术方案制备的电极在电解模拟天然海水中的选择性仅为50％，说明此方法制备的N-Co3O4/TM阳极的析氧选择性较差。(3) The N-Co3 O4 /TM prepared in step (1) was used as a working electrode, a platinum sheet was used as a counter electrode, and the simulated neutral natural seawater in step (4) in Example 1 was used as an electrolyte. The selectivity of N-Co3 O4 /TM was tested at current densities of 20, 40, 60, 80, and 100 mA/cm2. The selectivity of the electrode prepared by the technical solution provided in this comparative example in the electrolysis of simulated natural seawater was only 50%, indicating that the oxygen evolution selectivity of the N-Co3 O4 /TM anode prepared by this method was poor.
对比例2Comparative Example 2
本对比例提供一种制氢阳极，具体制备步骤包括：This comparative example provides a hydrogen production anode, and the specific preparation steps include:
(1)将商用钛网裁成1cm×3cm的长条状，在2mol·L-1的盐酸溶液中超声处理3min，然后依次分别在去离子水和无水乙醇中超声清洗三次，空气中自然干燥备用，按照实施例1相同的方法制得阳极基体N-Co3O4/TM。(1) A commercial titanium mesh was cut into strips of 1 cm × 3 cm, ultrasonically treated in a 2 mol·L-1 hydrochloric acid solution for 3 min, then ultrasonically cleaned three times in deionized water and anhydrous ethanol respectively, and dried naturally in air for later use. The anode substrate N-Co3 O4 /TM was prepared in the same manner as in Example 1.
(2)称取10gNaOH、22.5g丁二酰亚胺、22.5g焦磷酸钠、2.5g硝酸银，溶于500mL去离子水中配置镀银电镀液。(2) Weigh 10 g of NaOH, 22.5 g of succinimide, 22.5 g of sodium pyrophosphate, and 2.5 g of silver nitrate, and dissolve them in 500 mL of deionized water to prepare a silver plating solution.
(3)将烘干后的N-Co3O4/TM电极片置于(2)配置好的电镀液中进行电镀，优选镀银条件为5mAcm-2电流密度下电镀1min，得到Ag@N-Co3O4/TM析氧阳极。(3) Placing the dried N-Co3 O4 /TM electrode sheet in the electroplating solution prepared in (2) for electroplating, preferably the silver plating condition is electroplating for 1 min at a current density of 5 mA cm-2 to obtain Ag@N-Co3 O4 /TM oxygen evolution anode.
(4)称取29.22g氯化钠固体溶解于1L的去离子水中配制0.5M NaCl模拟中性天然海水溶液作为电解质溶液备用。(4) Weigh 29.22 g of sodium chloride solid and dissolve it in 1 L of deionized water to prepare a 0.5 M NaCl simulated neutral natural seawater solution as an electrolyte solution for later use.
(5)将步骤(3)中制备的Ag@N-Co3O4/TM作为工作电极，以铂片作为对电极，以步骤(4)中的模拟中性天然海水为电解质，在20、40、60、80、100mA/cm2的电流密度下测试Ag@N-Co3O4/TM的选择性，采用本对比例提供的技术方案制备的电极在电解模拟天然海水中的选择性仅为55％，说明此方法制备的Ag@N-Co3O4/TM阳极选择性较差。(5) The Ag@N-Co3 O4 /TM prepared in step (3) was used as the working electrode, the platinum sheet was used as the counter electrode, and the simulated neutral natural seawater in step (4) was used as the electrolyte. The selectivity of Ag@N-Co3 O4 /TM was tested at current densities of 20, 40, 60, 80, and 100 mA/cm2. The selectivity of the electrode prepared by the technical solution provided in this comparative example in the electrolysis of simulated natural seawater was only 55%, indicating that the Ag@N-Co3 O4 /TM anode prepared by this method had poor selectivity.
本对比例与实施例2大体相似，区别仅在于电镀时间参数的不同，显然，本对比例未形成实施例的银纳米层结构，其在模拟天然海水中的选择性较差，远低于实施例2采用的技术方案得到的选择性。This comparative example is generally similar to Example 2, and the only difference is the electroplating time parameter. Obviously, this comparative example does not form the silver nanolayer structure of the example, and its selectivity in simulated natural seawater is poor, which is far lower than the selectivity obtained by the technical solution adopted in Example 2.
对比例3Comparative Example 3
本实施例提供一种制氢阳极，具体制备步骤包括：This embodiment provides a hydrogen production anode, and the specific preparation steps include:
(1)将商用钛网裁成1cm×3cm的长条状，在2mol·L-1的盐酸溶液中超声处理3min，然后依次分别在去离子水和无水乙醇中超声清洗三次，空气中自然干燥备用，按照实施例1相同的方法制得阳极基体Co(OH)2/TM。(1) A commercial titanium mesh was cut into strips of 1 cm × 3 cm, ultrasonically treated in a 2 mol·L-1 hydrochloric acid solution for 3 min, then ultrasonically cleaned three times in deionized water and anhydrous ethanol respectively, and dried naturally in air for later use. The anode substrate Co(OH)2 /TM was prepared in the same manner as in Example 1.
(2)将制得的阳极基体Co(OH)2/TM在空气气氛下以350℃退火2小时，得到Co3O4/TM阳极。并通过实施例1中沉积银步骤得到Ag@Co3O4/TM(2) The prepared anode substrate Co(OH)2 /TM was annealed at 350°C for 2 hours in air atmosphere to obtain Co3 O4 /TM anode. And the Ag@Co3 O4 /TM was obtained by the silver deposition step in Example 1.
(3)称取29.22g氯化钠固体溶解于1L的去离子水中配制0.5M NaCl模拟中性天然海水溶液作为电解质溶液备用。(3) Weigh 29.22 g of sodium chloride solid and dissolve it in 1 L of deionized water to prepare a 0.5 M NaCl simulated neutral natural seawater solution as an electrolyte solution for later use.
(4)将步骤(2)中制备的Ag@Co3O4/TM作为工作电极，以铂片作为对电极，以步骤(3)中的模拟天然海水为电解质，在20、40、60、80、100mA/cm2的电流密度下测试Ag@N-Co3O4/TM的选择性，采用本对比例提供的技术方案制备的电极在电解模拟中性天然海水中的选择性约为70％，说明此方法制备的Ag@Co3O4/TM电极相较于Ag@N-Co3O4/TM阳极的析氧选择性较差，但沉积银颗粒后对于选择性有一定提升。(4) The Ag@Co3 O4 /TM prepared in step (2) was used as the working electrode, the platinum sheet was used as the counter electrode, and the simulated natural seawater in step (3) was used as the electrolyte. The selectivity of Ag@N-Co3 O4 /TM was tested at current densities of 20, 40, 60, 80, and 100 mA/cm2. The selectivity of the electrode prepared by the technical solution provided in this comparative example in the electrolysis of simulated neutral natural seawater was about 70%, indicating that the Ag@Co3 O4 /TM electrode prepared by this method had poor oxygen evolution selectivity compared with the Ag@N-Co3 O4 /TM anode, but the selectivity was improved to a certain extent after the deposition of silver particles.
对比例4Comparative Example 4
本实施例提供一种制氢阳极，具体制备步骤包括：This embodiment provides a hydrogen production anode, and the specific preparation steps include:
(1)将商用钛网裁成1cm×3cm的长条状，在2mol·L-1的盐酸溶液中超声处理3min，然后依次分别在去离子水和无水乙醇中超声清洗三次，空气中自然干燥备用，按照实施例1相同的方法制得阳极基体Co(OH)2/TM。(1) A commercial titanium mesh was cut into strips of 1 cm × 3 cm, ultrasonically treated in a 2 mol·L-1 hydrochloric acid solution for 3 min, then ultrasonically cleaned three times in deionized water and anhydrous ethanol respectively, and dried naturally in air for later use. The anode substrate Co(OH)2 /TM was prepared in the same manner as in Example 1.
(2)将制得的阳极基体Co(OH)2/TM在空气气氛下以350℃退火2小时，得到Co3O4/TM阳极。(2) The prepared anode substrate Co(OH)2 /TM was annealed at 350° C. for 2 hours in an air atmosphere to obtain a Co3 O4 /TM anode.
(3)称取29.22g氯化钠固体溶解于1L的去离子水中配制0.5M NaCl模拟中性天然海水溶液作为电解质溶液备用。(3) Weigh 29.22 g of sodium chloride solid and dissolve it in 1 L of deionized water to prepare a 0.5 M NaCl simulated neutral natural seawater solution as an electrolyte solution for later use.
(4)将步骤(2)中制备的Co3O4/TM作为工作电极，以铂片作为对电极，以步骤(3)中的模拟天然海水为电解质，在20、40、60、80、100mA/cm2的电流密度下测试Co3O4/TM的选择性，采用本对比例提供的技术方案制备的电极在电解模拟中性天然海水中的析氧选择性约为50％，说明此方法制备的Co3O4/TM电极的析氧选择性较差。(4) The Co3 O4 /TM prepared in step (2) was used as a working electrode, a platinum sheet was used as a counter electrode, and the simulated natural seawater in step (3) was used as an electrolyte. The selectivity of Co3 O4 /TM was tested at current densities of 20, 40, 60, 80, and 100 mA/cm2. The electrode prepared by the technical solution provided in this comparative example had an oxygen evolution selectivity of about 50% in the electrolysis of simulated neutral natural seawater, indicating that the oxygen evolution selectivity of the Co3 O4 /TM electrode prepared by this method was poor.
对比例5Comparative Example 5
本实施例提供一种制氢阳极，具体制备步骤包括：This embodiment provides a hydrogen production anode, and the specific preparation steps include:
(1)将商用钛网裁成1cm×3cm的长条状，在2mol·L-1的盐酸溶液中超声处理3min，然后依次分别在去离子水和无水乙醇中超声清洗三次，空气中自然干燥备用，按照实施例1相同的方法将Co(NO3)2溶液替换为Ni(NO3)2制得阳极基体Ni(OH)2/TM。(1) A commercial titanium mesh was cut into strips of 1 cm × 3 cm, ultrasonically treated in a 2 mol·L-1 hydrochloric acid solution for 3 min, and then ultrasonically cleaned three times in deionized water and anhydrous ethanol respectively, and dried naturally in air for later use. The anode substrate Ni(OH)2 /TM was prepared by the same method as in Example 1 except that the Co(NO3 )2 solution was replaced with Ni(NO3 )2 .
(2)将制得的阳极基体Ni(OH)2/TM在空气气氛下以350℃退火2小时，得到NiO/TM阳极。(2) The prepared anode substrate Ni(OH)2 /TM was annealed at 350° C. for 2 hours in an air atmosphere to obtain a NiO/TM anode.
(3)称取29.22g氯化钠固体溶解于1L的去离子水中配制0.5M NaCl模拟天然海水溶液作为电解质溶液备用。(3) Weigh 29.22 g of sodium chloride solid and dissolve it in 1 L of deionized water to prepare a 0.5 M NaCl simulated natural seawater solution as an electrolyte solution for later use.
(4)将步骤(2)中制备的NiO/TM作为工作电极，以铂片作为对电极，以步骤(3)中的模拟天然海水为电解质，在20、40、60、80、100mA/cm2的电流密度下测试NiO/TM的选择性，采用本对比例提供的技术方案制备的电极在电解模拟天然海水中的选择性约为35％，说明此方法制备的NiO/TM电极析氧选择性较差。(4) The NiO/TM prepared in step (2) was used as the working electrode, the platinum sheet was used as the counter electrode, and the simulated natural seawater in step (3) was used as the electrolyte. The selectivity of NiO/TM was tested at current densities of 20, 40, 60, 80, and 100 mA/cm2 . The selectivity of the electrode prepared by the technical solution provided in this comparative example in the electrolysis of simulated natural seawater was about 35%, indicating that the NiO/TM electrode prepared by this method had poor oxygen evolution selectivity.
对比例6Comparative Example 6
本实施例提供一种制氢阳极，具体制备步骤包括：This embodiment provides a hydrogen production anode, and the specific preparation steps include:
(1)将商用钛网裁成1cm×3cm的长条状，在2mol·L-1的盐酸溶液中超声处理3min，然后依次分别在去离子水和无水乙醇中超声清洗三次，空气中自然干燥备用，按照实施例1相同的方法将Co(NO3)2溶液替换为Ni(NO3)2制得阳极基体Ni(OH)2/TM。(1) A commercial titanium mesh was cut into strips of 1 cm × 3 cm, ultrasonically treated in a 2 mol·L-1 hydrochloric acid solution for 3 min, and then ultrasonically cleaned three times in deionized water and anhydrous ethanol respectively, and dried naturally in air for later use. The anode substrate Ni(OH)2 /TM was prepared by the same method as in Example 1 except that the Co(NO3 )2 solution was replaced with Ni(NO3 )2 .
(2)将制得的阳极基体Ni(OH)2/TM在空气气氛下以350℃退火2小时，得到NiO/TM阳极。并通过实施例1中沉积银颗粒的方法得到Ag@NiO/TM。(2) The prepared anode substrate Ni(OH)2 /TM was annealed at 350° C. for 2 hours in air atmosphere to obtain a NiO/TM anode. And Ag@NiO/TM was obtained by the method of depositing silver particles in Example 1.
(3)称取29.22g氯化钠固体溶解于1L的去离子水中配制0.5M NaCl模拟天然海水溶液作为电解质溶液备用。(3) Weigh 29.22 g of sodium chloride solid and dissolve it in 1 L of deionized water to prepare a 0.5 M NaCl simulated natural seawater solution as an electrolyte solution for later use.
(4)将步骤(2)中制备的Ag@NiO/TM作为工作电极，以铂片作为对电极，以步骤(3)中的模拟天然海水为电解质，在20、40、60、80、100mA/cm2的电流密度下测试Ag@NiO/TM的选择性，采用本对比例提供的技术方案制备的电极在电解模拟天然海水中的选择性约为60％，说明此方法制备的Ag@NiO/TM电极析氧选择性较差，但沉积银颗粒后对于选择性有一定提升。(4) The Ag@NiO/TM prepared in step (2) was used as a working electrode, a platinum sheet was used as a counter electrode, and the simulated natural seawater in step (3) was used as an electrolyte. The selectivity of Ag@NiO/TM was tested at current densities of 20, 40, 60, 80, and 100 mA/cm2 . The selectivity of the electrode prepared by the technical solution provided in this comparative example in the electrolysis of simulated natural seawater was about 60%, indicating that the Ag@NiO/TM electrode prepared by this method had poor oxygen evolution selectivity, but the selectivity was improved to a certain extent after the deposition of silver particles.
将实施例1、实施例2和对比例1、对比例2分别进行对比，对比例1未经过镀银工艺，在催化层表面没有进行排氯层，对比例2镀银的电镀时间较短，结果显示，实施例1和实施例2的技术方案明显由于对比例1和对比例2。Example 1 and Example 2 were compared with Comparative Example 1 and Comparative Example 2 respectively. Comparative Example 1 did not undergo the silver plating process and did not have a chlorine-removal layer on the surface of the catalytic layer. The silver plating time of Comparative Example 2 was shorter. The results showed that the technical solutions of Example 1 and Example 2 were significantly superior to those of Comparative Example 1 and Comparative Example 2.
基于上述实施例和对比例的结果分析可知，采用本发明所提供的方法，得到的阳极的表面抵抗氯离子的能力更强，从而显著提升阳极析氧的选择性。制备的Ag@N-Co3O4//TM催化剂阳极在含氯离子水溶液中，尤其是天然海水中电解制氢反应中具有优异的析氧选择性。Based on the results of the above examples and comparative examples, it can be seen that the surface of the anode obtained by the method provided by the present invention has a stronger ability to resist chloride ions, thereby significantly improving the selectivity of oxygen evolution at the anode. The prepared Ag@N-Co3 O4 //TM catalyst anode has excellent oxygen evolution selectivity in the electrolytic hydrogen production reaction in a chloride ion-containing aqueous solution, especially in natural seawater.
本发明通过简单的电镀/退火制备了致密包覆于导电基底上的N-Co3O4/TM析氧催化剂，并电镀/化学镀/氧化还原镀银层，采用非贵金属作为催化剂金属源，具有低成本的优势。本方法制备的Ag@N-Co3O4/TM电解中性天然海水析氧催化剂可以有效提高阳极析氧的选择性，在催化电解海水析氧反应中具有优良的稳定性。The present invention prepares a N-Co3 O4 /TM oxygen evolution catalyst densely coated on a conductive substrate by simple electroplating/annealing, and electroplating/chemical plating/oxidation-reduction silver plating layer, and uses non-precious metals as catalyst metal sources, which has the advantage of low cost. The Ag@N-Co3 O4 /TM electrolysis neutral natural seawater oxygen evolution catalyst prepared by this method can effectively improve the selectivity of anode oxygen evolution and has excellent stability in the catalytic electrolysis of seawater oxygen evolution reaction.
以上仅为本发明的优选实施例而已，其并非因此限制本发明的保护范围，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，通过常规的替代或者能够实现相同的功能在不脱离本发明的原理和精神的情况下对这些实施例进行变化、修改、替换、整合和参数变更均落入本发明的保护范围内。The above are only preferred embodiments of the present invention, which do not limit the protection scope of the present invention. For those skilled in the art, the present invention may have various modifications and changes. Within the spirit and principle of the present invention, changes, modifications, replacements, integrations and parameter changes to these embodiments by conventional substitutions or by being able to achieve the same functions without departing from the principles and spirit of the present invention all fall within the protection scope of the present invention.
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| CN202310686550.2ACN117888131B (en) | 2023-06-09 | 2023-06-09 | Hydrogen production anode by electrolyzing natural seawater and preparation method and application thereof |
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