技术领域technical field
本发明涉及海水氧化催化剂技术领域，具体是一种铁和钼共同修饰的硫化镍纳米片阵列及其制备方法和应用。The invention relates to the technical field of seawater oxidation catalysts, in particular to a nickel sulfide nanosheet array co-decorated with iron and molybdenum, a preparation method and application thereof.
背景技术Background technique
电解水制氢技术不仅可以制备高纯度的氢气，而且能够直接使用间歇性的风能或太阳能等可再生能源产生的电能，是一种有前景、可持续的高纯度制氢技术。近年来，人们致力于开发高性能的非贵金属催化剂来提高电解槽的效率，有些催化剂甚至已经达到了比贵金属催化剂更好的性能。然而，电解槽的大规模使用将加重淡水资源紧缺的压力。考虑到海水在地球的资源丰富，开发直接电解海水技术不仅取材方便，而且能够与沿海发电设备直接联用，是一项非常有前景的技术。然而，海水电解技术的实现仍然具有很高的挑战性，特别是对于阳极反应。首先，由于海水中存在着大量的氯离子(～0.5M)，阳极上容易触发两电子的析氯反应，从而影响四电子的析氧反应(OER)的选择性。在碱性介质中，Cl-离子会进一步与OH-反应形成次氯酸盐(ClO-)，该反应的热力学电位比OER高约480mV，因此需要开发高活性的OER催化剂以避免ClO-的形成(ChemSusChem,2016,9,962-972)。此外，在电解海水过程中，一些不溶性沉物质的沉积以及Cl-离子的腐蚀会对电极造成损害，影响其活性和稳定性(Angew.Chem.Int.Ed.,2022,61,e202210753)。Electrolyzed water hydrogen production technology can not only produce high-purity hydrogen, but also can directly use electricity generated by intermittent wind or solar energy and other renewable energy sources. It is a promising and sustainable high-purity hydrogen production technology. In recent years, efforts have been made to develop high-performance non-precious metal catalysts to improve the efficiency of electrolyzers, and some catalysts have even achieved better performance than noble metal catalysts. However, the large-scale use of electrolyzers will aggravate the pressure on the shortage of fresh water resources. Considering the abundance of seawater resources on the earth, the development of direct electrolysis seawater technology is not only convenient to obtain materials, but also can be directly used with coastal power generation equipment, which is a very promising technology. However, the realization of seawater electrolysis technology is still highly challenging, especially for the anodic reaction. First, due to the presence of a large amount of chloride ions (~0.5M) in seawater, the two-electron chlorine evolution reaction is easily triggered on the anode, thereby affecting the selectivity of the four-electron oxygen evolution reaction (OER). In alkaline media, Cl- ions will further react with OH- to form hypochlorite (ClO- ), the thermodynamic potential of this reaction is about 480 mV higher than OER, so it is necessary to develop highly active OER catalysts to avoid the formation of ClO- (ChemSusChem, 2016, 9, 962-972). In addition, during the electrolysis of seawater, the deposition of some insoluble sediments and the corrosion of Cl- ions will cause damage to the electrode, affecting its activity and stability (Angew.Chem.Int.Ed., 2022, 61, e202210753).
过渡金属硫化物(TMS)具有良好的电子结构和导电性，被广泛用作OER催化剂。最近的研究表明，TMS能够在OER过程中原位生成带负电荷的硫酸盐钝化层，通过排斥海水中的Cl-离子远离催化剂的界面，从而赋予催化剂优异的耐腐蚀性，有望用于大电流密度下电解海水制氢(Proc.Natl.Acad.Sci.USA,116,6624-6629)。然而，目前TMS的OER活性仍达不到大规模应用的要求，特别是在大电流密度下。在众多改性策略中，Fe金属原子修饰已被证明能够优化活性位点与OER中间物之间的作用强度(ACS Catal.,2021,11,5601-5613)，而Mo原子修饰则有助于构建多催化活性位点(Nano Energy,2021,87,106217)。尽管这两种金属原子都能提高OER活性，但是单种金属原子修饰的作用效果仍然有限。因此，如果同时使用这两种异质原子来修饰TMS(如Ni3S2)，不仅可以发挥每种金属单独修饰时的效果，而且异质原子之间的协同作用会引发“1+1＞2”的效果，从而大幅度提升Ni3S2的电解海水活性，促进电解海水阳极催化剂的发展。Transition metal sulfides (TMS) are widely used as OER catalysts due to their favorable electronic structures and electrical conductivity. Recent studies have shown that TMS is capable of in situ generating a negatively charged sulfate passivation layer during the OER process, which endows the catalyst with excellent corrosion resistance by repelling Cl- ions in seawater away from the interface of the catalyst, which is expected to be used for large currents. Hydrogen production by electrolysis of seawater under density (Proc. Natl. Acad. Sci. USA, 116, 6624-6629). However, the current OER activity of TMS still falls short of the requirements for large-scale applications, especially at high current densities. Among many modification strategies, Fe metal atom modification has been shown to be able to optimize the interaction strength between active sites and OER intermediates (ACS Catal., 2021, 11, 5601-5613), while Mo atom modification can help Construction of multiple catalytic active sites (Nano Energy, 2021, 87, 106217). Although both metal atoms can enhance the OER activity, the effect of single metal atom modification is still limited. Therefore, if these two kinds of heteroatoms are used to modify TMS (such as Ni3S2), not only can the effect of each metal be modified individually, but also the synergistic effect between heteroatoms will trigger the "1+1>2" effect, thereby greatly improving the electrolytic seawater activity of Ni3 S2 and promoting the development of electrolytic seawater anode catalysts.
发明内容Contents of the invention
本发明的目的在于提供一种硫化镍纳米片阵列及其制备方法和应用，以解决背景技术中提出的问题。The object of the present invention is to provide a nickel sulfide nanosheet array and its preparation method and application, so as to solve the problems raised in the background technology.
为实现上述目的，本发明提供如下技术方案：To achieve the above object, the present invention provides the following technical solutions:
一种铁和钼共同修饰的硫化镍纳米片阵列，该材料为生长在泡沫镍基底上的铁和钼共同修饰的硫化镍纳米片阵列，其中，铁原子含量为2.45％～10.76％，钼原子含量为1.11％～8.99％。A nickel sulfide nanosheet array co-modified with iron and molybdenum, the material is a nickel sulfide nanosheet array co-modified with iron and molybdenum grown on a nickel foam substrate, wherein the content of iron atoms is 2.45% to 10.76%, molybdenum atoms The content is 1.11% to 8.99%.
在上述技术方案的基础上，本发明还提供以下可选技术方案：On the basis of the above technical solutions, the present invention also provides the following optional technical solutions:
在一种可选方案中：铁和钼共同修饰的硫化镍纳米片阵列由表面粗糙的纳米片堆积而成，且每个纳米片由30-80nm的纳米颗粒组装而成。In an alternative solution: the nickel sulfide nanosheet array co-decorated with iron and molybdenum is formed by stacking nanosheets with rough surfaces, and each nanosheet is assembled by nanoparticles of 30-80 nm.
一种铁和钼共同修饰的硫化镍纳米片阵列的制备方法，包括以下步骤：步骤S1：采用水热法制备得到氢氧化镍纳米片阵列作为自模板；步骤S2：在水热过程中将氢氧化镍转变为硫化镍，同时将铁和钼原子共同修饰到硫化镍纳米片阵列中。A method for preparing a nickel sulfide nanosheet array co-decorated with iron and molybdenum, comprising the following steps: step S1: using a hydrothermal method to prepare a nickel hydroxide nanosheet array as a self-template; step S2: adding hydrogen Nickel oxide is transformed into nickel sulfide, while iron and molybdenum atoms are co-decorated into nickel sulfide nanosheet arrays.
在一种可选方案中：所述步骤S1的具体步骤是：将清洗干净的泡沫镍置于60mL含有0.05mol/L Ni(NO3)2·6H2O、0.167mol/L尿素和0.067mol/L氟化铵的澄清溶液中，利用溶剂热法在120℃的条件下反应6h，反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的氢氧化镍纳米片阵列。In an alternative: the specific steps of step S1 are: placing the cleaned nickel foam in 60mL containing 0.05mol/L Ni(NO3 )2 6H2 O, 0.167mol/L urea and 0.067mol /L ammonium fluoride clarified solution, using the solvothermal method to react at 120°C for 6 hours, after the reaction is completed and cooled to room temperature, rinse and dry in an oven to obtain nickel hydroxide grown on nickel foam Nanosheet arrays.
在一种可选方案中：所述步骤S2的具体步骤是：将氢氧化镍纳米片阵列置于含有硫脲、Fe3+和MoO42-的溶液中进行水热反应得到铁和钼共同修饰的硫化镍纳米片阵列。In an optional scheme: the specific steps of the step S2 are: placing the nickel hydroxide nanosheet array in a solution containing thiourea, Fe3+ and MoO42- to carry out a hydrothermal reaction to obtain iron and molybdenum Modified nickel sulfide nanosheet arrays.
在一种可选方案中：所述硫脲的浓度为0.01～0.10mol/L，所述的Fe3+由浓度为0.01～0.10mol/L的Fe(NO3)3、Fe2(SO4)3或FeCl3提供；所述的MoO42-是由浓度为0.005～0.08mol/L的Na2MoO4或K2MoO4提供。In an optional solution: the concentration of the thiourea is 0.01-0.10 mol/L, and the Fe3+ is composed of Fe(NO3 )3 , Fe2 (SO4 )3 or FeCl3 ; the MoO42- is provided by Na2 MoO4 or K2 MoO4 with a concentration of 0.005-0.08 mol/L.
在一种可选方案中：所述水热法中水热反应条件为100～160℃，反应8～20h。In an optional solution: the hydrothermal reaction condition in the hydrothermal method is 100-160° C., and the reaction is 8-20 hours.
基于上述所述的铁和钼共同修饰的硫化镍纳米片阵列在碱性水或海水的氧化反应中的应用。The application of nickel sulfide nanosheet arrays co-modified with iron and molybdenum in the oxidation reaction of alkaline water or seawater based on the above.
在一种可选方案中：铁和钼共同修饰的硫化镍纳米片阵列在碱性水或海水的氧化反应中的具体应用方法为：将铁和钼共同修饰的硫化镍纳米片阵列置于碱性体系中作为析氧电极，用于碱性水和海水的氧化反应。In an optional scheme: the specific application method of the nickel sulfide nanosheet array decorated with iron and molybdenum in the oxidation reaction of alkaline water or seawater is: the nickel sulfide nanosheet array decorated with iron and molybdenum is placed in an alkali It can be used as an oxygen evolution electrode in a neutral system for the oxidation reaction of alkaline water and seawater.
相较于现有技术，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
1、本发明创新性地开发了独特的两步水热法，利用氢氧化镍纳米片作为自模板，将其转变为硫化镍的同时引入铁和钼原子，形成铁和钼共同修饰的硫化镍纳米片阵列，制备方法简单高效。该样品为生长在泡沫镍基底上、由30～80nm的纳米颗粒组成的粗糙纳米片阵列，能够充分暴露活性位点。同时，铁和钼共同修饰有利于增强硫化镍的导电性，提高电子的转移能力，从而促进析氧反应的反应动力学，最终显著提高电极的海水氧化性能；1. The present invention innovatively develops a unique two-step hydrothermal method, using nickel hydroxide nanosheets as a self-template, converting it into nickel sulfide while introducing iron and molybdenum atoms to form nickel sulfide co-modified by iron and molybdenum The nanosheet array has a simple and efficient preparation method. The sample is a rough nanosheet array composed of 30-80nm nanoparticles grown on a nickel foam substrate, which can fully expose active sites. At the same time, the co-modification of iron and molybdenum is beneficial to enhance the conductivity of nickel sulfide, improve the electron transfer ability, thereby promoting the reaction kinetics of oxygen evolution reaction, and finally significantly improving the seawater oxidation performance of the electrode;
2、本发明提供的铁和钼共同修饰的硫化镍纳米片阵列作为碱性水和海水氧化电极，展示出了优异的催化活性和稳定性。在10、100和500mA cm-2的电流密度下，在碱性水溶液中所需的过电势低至194、236和276mV，在碱性海水中所需的过电位为201、251和308mV，远低于单独的铁修饰硫化镍和硫化镍样品。同时，该催化剂在100和500mA cm-2的恒定电流密度下分别运行1200和900个小时，其海水氧化性能没有明显衰减。该性能优于已经报道的绝大部分非贵金属催化剂。2. The nickel sulfide nanosheet arrays co-decorated with iron and molybdenum provided by the present invention are used as oxidation electrodes for alkaline water and seawater, and exhibit excellent catalytic activity and stability. At current densities of 10, 100, and 500 mA cm-2 , the required overpotentials were as low as 194, 236, and 276 mV in alkaline aqueous solutions, and 201, 251, and 308 mV in alkaline seawater, far from lower than that of iron-modified nickel sulfide and nickel sulfide samples alone. At the same time, the catalyst operated at a constant current density of 100 and 500mA cm-2 for 1200 and 900 hours, respectively, and its seawater oxidation performance did not decay significantly. This performance is superior to most of the reported non-precious metal catalysts.
附图说明Description of drawings
图1为第一次水热反应后生长在泡沫镍基底上的氢氧化镍(记为Ni(OH)2)纳米片阵列不同倍率的扫描电子显微镜(SEM)图像。Fig. 1 is a scanning electron microscope (SEM) image at different magnifications of nickel hydroxide (referred to as Ni(OH)2 ) nanosheet arrays grown on a nickel foam substrate after the first hydrothermal reaction.
图2为第二次水热反应后生长在泡沫镍基底上的铁和钼共同修饰的硫化镍(记为FeMo-Ni3S2)纳米片阵列不同倍率的SEM图像。Fig. 2 is the SEM images of different magnifications of nickel sulfide (referred to as FeMo-Ni3 S2 ) nanosheet arrays co-modified by iron and molybdenum grown on the nickel foam substrate after the second hydrothermal reaction.
图3为FeMo-Ni3S2的Ni、S、Fe和Mo元素的分布图。Fig. 3 is a distribution diagram of Ni, S, Fe and Mo elements in FeMo-Ni3 S2 .
图4(a)为Ni(OH)2的XRD图；(b)～(c)为FeMo-Ni3S2、Fe-Ni3S2和Ni3S2的XRD对比图；(d)为FeMo-Ni3S2、Fe-Ni3S2和Ni3S2的拉曼光谱对比图。Figure 4(a) is the XRD pattern of Ni(OH)2 ; (b)~(c) is the XRD comparison pattern of FeMo-Ni3 S2 , Fe-Ni3 S2 and Ni3 S2 ; (d) is Comparison of Raman spectra of FeMo-Ni3 S2 , Fe-Ni3 S2 and Ni3 S2 .
图5为FeMo-Ni3S2在碱性电解液(1M KOH)中与其他样品的OER性能对比图：(a)线性扫描伏安(LSV)曲线；(b)不同电流密度下的过电势对比图；(c)塔菲尔(Tafel)图；(d)电化学阻抗谱(EIS)。Figure 5 is a comparison of the OER performance of FeMo-Ni3 S2 in alkaline electrolyte (1M KOH) and other samples: (a) linear sweep voltammetry (LSV) curve; (b) overpotential at different current densities Comparison diagram; (c) Tafel diagram; (d) electrochemical impedance spectroscopy (EIS).
图6为FeMo-Ni3S2碱性海水电解液(1M KOH海水)中与其他样品的OER性能对比图：(a)LSV曲线；(b)不同电流密度下的过电势对比图；(c)在不同电流密度下稳定测试的性能曲线。Figure 6 is a comparison of OER performance between FeMo-Ni3 S2 alkaline seawater electrolyte (1M KOH seawater) and other samples: (a) LSV curve; (b) comparison of overpotential at different current densities; (c ) Performance curves of stable tests at different current densities.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。本发明所列举的各实施例仅用以说明本发明，并非用以限制本发明的范围。对本发明所作的任何显而易知的修饰或变更都不脱离本发明的精神与范围。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. The various embodiments listed in the present invention are only used to illustrate the present invention, and are not intended to limit the scope of the present invention. Any obvious modifications or changes made to the present invention do not depart from the spirit and scope of the present invention.
实施例1Example 1
本发明实施例公布了一种铁和钼共同修饰的硫化镍纳米片阵列，该材料为生长在泡沫镍基底上的铁和钼共同修饰的硫化镍纳米片阵列，其中，铁原子含量为2.45％～10.76％，钼原子含量为1.11％～8.99％；硫化镍纳米片阵列由表面粗糙的纳米片堆积而成，且每个纳米片由30-80nm的纳米颗粒组装而成。The embodiment of the present invention discloses a nickel sulfide nanosheet array co-modified with iron and molybdenum. The material is a nickel sulfide nanosheet array co-modified with iron and molybdenum grown on a nickel foam substrate, wherein the content of iron atoms is 2.45%. ～10.76%, molybdenum atom content is 1.11%～8.99%; nickel sulfide nanosheet array is formed by stacking nanosheets with rough surface, and each nanosheet is assembled by 30-80nm nanoparticles.
本发明实施例还公布了铁和钼共同修饰的硫化镍纳米片阵列的制备方法，该方法的步骤如下：The embodiment of the present invention also discloses a method for preparing nickel sulfide nanosheet arrays co-modified by iron and molybdenum. The steps of the method are as follows:
(1)将清洗干净的泡沫镍置于60mL含有0.05mol/L Ni(NO3)2·6H2O、0.167mol/L尿素和0.067mol/L氟化铵的澄清溶液中，利用溶剂热法在120℃的条件下反应6h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的氢氧化镍(记为Ni(OH)2)纳米片阵列。(1) Place the cleaned nickel foam in 60mL of a clear solution containing 0.05mol/L Ni(NO3 )2 6H2 O, 0.167mol/L urea and 0.067mol/L ammonium fluoride, and use solvothermal method The reaction was carried out at 120°C for 6h. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel hydroxide (referred to as Ni(OH)2 ) nanosheet array grown on the nickel foam.
(2)利用第二次水热方法将氢氧化镍转化为硫化镍，同时将Fe、Mo原子引入；依次将0.033mol/L硫脲、0.05mol/L Fe(NO3)2·9H2O和0.013mol/LNa2MoO4·2H2O溶解于60mL的去离子水中，并搅拌反应约30min。将氢氧化镍纳米片阵列置于该澄清溶液中，利用溶剂热法在120℃的条件下反应12h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的铁和钼共同修饰的硫化镍(记为FeMo-Ni3S2)纳米片阵列。(2) Use the second hydrothermal method to convert nickel hydroxide into nickel sulfide, and at the same time introduce Fe and Mo atoms; sequentially add 0.033mol/L thiourea, 0.05mol/L Fe(NO3 )2 ·9H2 O and 0.013mol/L Na2 MoO4 ·2H2 O were dissolved in 60 mL of deionized water, and stirred for about 30 min. The nickel hydroxide nanosheet array was placed in the clear solution, and reacted at 120° C. for 12 h by solvothermal method. After the reaction was completed and cooled to room temperature, it was rinsed and dried in an oven to obtain an array of nickel sulfide (referred to as FeMo-Ni3 S2 ) co-decorated with iron and molybdenum grown on the nickel foam.
(3)将制备得到的铁和钼共同修饰的硫化镍纳米片阵列作为工作电极、氧化汞电极为参比电极、石墨棒电极为对电极构成三电极体系置于碱性海水溶液中测试其海水氧化性能。(3) The prepared nickel sulfide nanosheet array co-modified with iron and molybdenum was used as the working electrode, the mercury oxide electrode was used as the reference electrode, and the graphite rod electrode was used as the counter electrode to form a three-electrode system, which was placed in alkaline seawater solution to test its seawater Oxidation properties.
图1展示了Ni(OH)2不同倍率的SEM图像，可以发现泡沫镍基底上生长了均匀且光滑的纳米片阵列，厚度为10～30nm。Figure 1 shows the SEM images of Ni(OH)2 at different magnifications. It can be found that a uniform and smooth nanosheet array grows on the foamed nickel substrate with a thickness of 10-30nm.
图2为FeMo-Ni3S2不同倍率的SEM图像，可以发现纳米片的框架基本保持，但是原先光滑的纳米片变得非常粗糙，由非常小的纳米颗粒(30～80nm)组成，这是因为在第二步水热过程中，羟基被S原子取代形成硫化镍，同时引入Fe和Mo原子，最终形成Fe和Mo共修饰的Ni3S2粗糙的纳米片阵列。Figure 2 is the SEM images of FeMo-Ni3 S2 at different magnifications. It can be found that the framework of the nanosheets is basically maintained, but the original smooth nanosheets become very rough and consist of very small nanoparticles (30-80nm), which is Because in the second hydrothermal process, the hydroxyl groups were replaced by S atoms to form nickel sulfide, and Fe and Mo atoms were introduced at the same time, finally forming Fe and Mo co-modified Ni3 S2 rough nanosheet arrays.
图3为TEM图像的EDX测试结果，Ni、Mo、Fe和S元素都均匀地分布在纳米片上，成功证明了硫化镍的形成以及Fe和Mo也被掺入到纳米片中。Figure 3 shows the EDX test results of the TEM image. Ni, Mo, Fe and S elements are uniformly distributed on the nanosheets, which successfully proves the formation of nickel sulfide and the incorporation of Fe and Mo into the nanosheets.
图4(a)的XRD图谱上的特征峰与Ni(PDF#4-850)和Ni(OH)2(PDF#3-177)相匹配，说明氢氧化镍的成功合成。在第二次水热反应后，图4(b)展示了Ni(OH)2的特征峰已经完全转变为Ni3S2(PDF#44-1418)，说明硫化镍的成功合成，而单独的Fe以及Fe和Mo共同修饰并没有改变Ni3S2的结构，而在FeMo-Ni3S2样品上观察到属于的FeMoO4的峰是由于在第二步水热过程中Fe3+和MoO42-反应形成的少量沉淀。进一步观察图4(c)局部放大的XRD对比图，相比于纯的Ni3S2样品，金属修饰后Ni3S2(110)的特征峰发生了明显的偏移，这是因为Fe、Mo和Ni原子之间不同的原子半径所导致，这也说明了Fe和Mo同时掺入到Ni3S2的晶格中。图4(d)展示了这三种样品的拉曼光谱对比，可以发现金属修饰后Ni3S2的特征峰发生了偏移，同时FeMo-Ni3S2样品上存在着Mo-O键，与XRD的结果相一致。综上所有表征，FeMo-Ni3S2样品的主要成分为少量的FeMoO4以及Fe和Mo共同掺杂的Ni3S2。The characteristic peaks on the XRD pattern of Figure 4(a) match with Ni (PDF #4-850) and Ni(OH)2 (PDF #3-177), indicating the successful synthesis of nickel hydroxide. After the second hydrothermal reaction, Fig. 4(b) shows that the characteristic peak of Ni(OH)2 has been completely transformed into Ni3 S2 (PDF#44-1418), indicating the successful synthesis of nickel sulfide, while the single Fe and the co-modification of Fe and Mo did not change the structure of Ni3 S2 , while the peak belonging to FeMoO4 observed on the FeMo-Ni3 S2 sample was due to the addition of Fe3+ and MoO in the second hydrothermal process42- Reaction formed a small amount of precipitate. Further observation of the partially enlarged XRD comparison diagram in Figure 4(c), compared with the pure Ni3 S2 sample, the characteristic peaks of Ni3 S2 (110) after metal modification have shifted significantly, because Fe, This is caused by the different atomic radii between Mo and Ni atoms, which also explains the simultaneous incorporation of Fe and Mo intotheNi3S2 lattice. Figure 4(d) shows the comparison of the Raman spectra of these three samples. It can be found that the characteristic peaks of Ni3 S2 have shifted after metal modification, and there are Mo-O bonds on the FeMo-Ni3 S2 samples. Consistent with the results of XRD. To sum up all the above characterizations, the main components of the FeMo-Ni3 S2 sample are a small amount of FeMoO4 and Ni3 S2 co-doped with Fe and Mo.
图5(a)和(b)分别展示了FeMo-Ni3S2、Fe-Ni3S2、Ni3S2和商用IrO2样品在1M KOH溶液中的线性扫描伏安(LSV)曲线以及详细的OER过电势对比图。对比于其他样品，FeMo-Ni3S2样品拥有显著提升的OER性能，分别在10、100和500mA cm-2的电流密度下，所需的OER过电势仅低至194、236和276mV，远优于商用的IrO2样品。进一步计算这些了样品的塔菲尔斜率如图5(c)所示，FeMo-Ni3S2的塔菲尔斜率比其他样品小的多，为38.3mV dec-1，说明Fe和Mo共同修饰有利于促进更加快速的OER反应动力学。同时，Fe和Mo共同修饰也有利于提高Ni3S2的导电性，从而促进催化剂上快速的电子转移，正如图5(d)的电化学阻抗图上FeMo-Ni3S2最小的电荷转移电阻所示。Figure 5(a)and(b) show the linear sweep voltammetry( LSV) curves and Detailed OER overpotential comparison diagram. Compared with other samples, the FeMo-Ni3 S2 sample has significantly improved OER performance, and the required OER overpotentials are only as low as 194, 236 and 276mV at current densities of 10, 100 and 500mA cm-2 , far from Outperforms commercialIrO2 samples. Further calculation of the Tafel slopes of these samples is shown in Figure 5(c), the Tafel slope of FeMo-Ni3 S2 is much smaller than other samples, at 38.3mV dec-1 , indicating that Fe and Mo are co-modified It is beneficial to promote faster OER reaction kinetics. At the same time, the co-modification of Fe and Mo is also beneficial to improve the conductivity of Ni3 S2 , thereby promoting the rapid electron transfer on the catalyst, just as the minimum charge transfer of FeMo-Ni3 S2 in the electrochemical impedance diagram of Figure 5(d) resistance shown.
图6展示了这些样品在1M KOH海水中的电化学性能测试结果。图6(a)和(b)分别展示了FeMo-Ni3S2、Fe-Ni3S2、Ni3S2样品在1M KOH海水溶液中的LSV曲线以及相应的海水氧化过电势对比图。对比于其他样品，FeMo-Ni3S2样品拥有显著提升的海水氧化性能，分别在10、100和500mA cm-2的电流密度下，所需的OER过电势仅低至201、251和308mV。此外，正如图6(c)的稳定性测试结果所示，FeMo-Ni3S2样品在100和500mA cm-2的恒定电流密度下分别运行1200和900个小时，其海水氧化性能没有明显衰减。Figure 6 shows the electrochemical performance test results of these samples in 1M KOH seawater. Figure 6(a) and (b) respectively show the LSV curves of FeMo-Ni3 S2 , Fe-Ni3 S2 , and Ni3 S2 samples in 1M KOH seawater solution and the corresponding seawater oxidation overpotential comparison chart. Compared with other samples, the FeMo-Ni3 S2 sample has significantly improved seawater oxidation performance, and the required OER overpotentials are only as low as 201, 251, and 308 mV at current densities of 10, 100, and 500 mA cm-2 , respectively. In addition, as shown by the stability test results in Fig. 6(c), the seawater oxidation performance of the FeMo-Ni3 S2 sample was not significantly attenuated when operated at a constant current density of 100 and 500 mA cm-2 for 1200 and 900 hours, respectively .
实施例2Example 2
本发明实施例公布了一种铁和钼共同修饰的硫化镍纳米片阵列，该材料为生长在泡沫镍基底上的铁和钼共同修饰的硫化镍纳米片阵列，其中，铁原子2.45％～10.76％，钼原子含量为1.11～8.99％；硫化镍纳米片阵列由表面粗糙的纳米片堆积而成，且每个纳米片由30-80nm的纳米颗粒组装而成。The embodiment of the present invention discloses a nickel sulfide nanosheet array co-modified with iron and molybdenum. %, the content of molybdenum atoms is 1.11-8.99%; the nickel sulfide nano-sheet array is formed by stacking rough-surfaced nano-sheets, and each nano-sheet is assembled by 30-80nm nanoparticles.
本发明实施例还公布了铁和钼共同修饰的硫化镍纳米片阵列的制备方法，该方法的步骤如下：The embodiment of the present invention also discloses a method for preparing nickel sulfide nanosheet arrays co-modified by iron and molybdenum. The steps of the method are as follows:
(1)将清洗干净的泡沫镍置于60mL含有0.05mol/L Ni(NO3)2·6H2O、0.167mol/L尿素和0.067mol/L氟化铵的澄清溶液中，利用溶剂热法在120℃的条件下反应6h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的氢氧化镍纳米片阵列。(1) Place the cleaned nickel foam in 60mL of a clear solution containing 0.05mol/L Ni(NO3 )2 6H2 O, 0.167mol/L urea and 0.067mol/L ammonium fluoride, and use solvothermal method The reaction was carried out at 120°C for 6h. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel hydroxide nanosheet array grown on the nickel foam.
(2)利用第二次水热方法将氢氧化镍转化为硫化镍，同时将Fe、Mo原子引入。依次将0.01mol/L硫脲、0.01mol/L Fe(NO3)2·9H2O和0.005mol/LNa2MoO4·2H2O溶解于60mL的去离子水中，并搅拌反应约30min。将氢氧化镍纳米片阵列置于该澄清溶液中，利用溶剂热法在110℃的条件下反应16h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的铁和钼共同修饰的硫化镍纳米片阵列。(2) Using the second hydrothermal method to convert nickel hydroxide into nickel sulfide, while introducing Fe and Mo atoms. 0.01 mol/L thiourea, 0.01 mol/L Fe(NO3 )2 ·9H2 O and 0.005 mol/L Na2 MoO4 ·2H2 O were dissolved in 60 mL of deionized water in sequence, and the reaction was stirred for about 30 min. The nickel hydroxide nanosheet array was placed in the clear solution, and reacted at 110° C. for 16 h by solvothermal method. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel sulfide nanosheet array co-decorated with iron and molybdenum grown on the nickel foam.
(3)将制备得到的铁和钼共同修饰的硫化镍纳米片阵列作为工作电极、氧化汞电极为参比电极、石墨棒电极为对电极构成三电极体系置于碱性水和海水溶液中测试其海水氧化性能。该样品在10、100和500mA cm-2的电流密度时海水氧化的过电势如表1所示。(3) The prepared nickel sulfide nanosheet array co-modified with iron and molybdenum was used as the working electrode, the mercury oxide electrode was used as the reference electrode, and the graphite rod electrode was used as the counter electrode to form a three-electrode system, which was tested in alkaline water and seawater solution. Its seawater oxidation properties. Table 1 shows the overpotentials of seawater oxidation for this sample at current densities of 10, 100 and 500 mA cm-2 .
实施例3Example 3
本发明实施例公布了一种铁和钼共同修饰的硫化镍纳米片阵列，该材料为生长在泡沫镍基底上的铁和钼共同修饰的硫化镍纳米片阵列，其中，铁原子含量为2.45％～10.76％，钼原子含量为1.11％～8.99％；硫化镍纳米片阵列由表面粗糙的纳米片堆积而成，且每个纳米片由30-80nm的纳米颗粒组装而成。The embodiment of the present invention discloses a nickel sulfide nanosheet array co-modified with iron and molybdenum. The material is a nickel sulfide nanosheet array co-modified with iron and molybdenum grown on a nickel foam substrate, wherein the content of iron atoms is 2.45%. ～10.76%, molybdenum atom content is 1.11%～8.99%; nickel sulfide nanosheet array is formed by stacking nanosheets with rough surface, and each nanosheet is assembled by 30-80nm nanoparticles.
本发明实施例还公布了铁和钼共同修饰的硫化镍纳米片阵列的制备方法，该方法的步骤如下：The embodiment of the present invention also discloses a method for preparing nickel sulfide nanosheet arrays co-modified by iron and molybdenum. The steps of the method are as follows:
(1)将清洗干净的泡沫镍置于60mL含有0.05mol/L Ni(NO3)2·6H2O、0.167mol/L尿素和0.067mol/L氟化铵的澄清溶液中，利用溶剂热法在120℃的条件下反应6h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的氢氧化镍纳米片阵列。(1) Place the cleaned nickel foam in 60mL of a clear solution containing 0.05mol/L Ni(NO3 )2 6H2 O, 0.167mol/L urea and 0.067mol/L ammonium fluoride, and use solvothermal method The reaction was carried out at 120°C for 6h. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel hydroxide nanosheet array grown on the nickel foam.
(2)利用第二次水热方法将氢氧化镍转化为硫化镍，同时将Fe、Mo原子引入。依次将0.042mol/L硫脲、0.06mol/L FeCl3·6H2O和0.025mol/LNa2MoO4·2H2O溶解于60mL的去离子水中，并搅拌反应约30min。将氢氧化镍纳米片阵列置于该澄清溶液中，利用溶剂热法在140℃的条件下反应10h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的铁和钼共同修饰的硫化镍纳米片阵列。(2) Using the second hydrothermal method to convert nickel hydroxide into nickel sulfide, while introducing Fe and Mo atoms. Dissolve 0.042 mol/L thiourea, 0.06 mol/L FeCl3 ·6H2 O and 0.025 mol/L Na2 MoO4 ·2H2 O in 60 mL of deionized water in sequence, and stir for about 30 min. The nickel hydroxide nanosheet array was placed in the clear solution, and reacted at 140° C. for 10 h by solvothermal method. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel sulfide nanosheet array co-decorated with iron and molybdenum grown on the nickel foam.
(3)将制备得到的铁和钼共同修饰的硫化镍纳米片阵列作为工作电极、氧化汞电极为参比电极、石墨棒电极为对电极构成三电极体系置于碱性水和海水溶液中测试其海水氧化性能。该样品在10、100和500mA cm-2的电流密度时海水氧化的过电势如表1所示。(3) The prepared nickel sulfide nanosheet array co-modified with iron and molybdenum was used as the working electrode, the mercury oxide electrode was used as the reference electrode, and the graphite rod electrode was used as the counter electrode to form a three-electrode system, which was tested in alkaline water and seawater solution. Its seawater oxidation properties. Table 1 shows the overpotentials of seawater oxidation for this sample at current densities of 10, 100 and 500 mA cm-2 .
实施例4Example 4
本发明实施例公布了一种铁和钼共同修饰的硫化镍纳米片阵列，该材料为生长在泡沫镍基底上的铁和钼共同修饰的硫化镍纳米片阵列，其中，铁原子含量为2.45％～10.76％，钼原子含量为1.11％～8.99％；硫化镍纳米片阵列由表面粗糙的纳米片堆积而成，且每个纳米片由30-80nm的纳米颗粒组装而成。The embodiment of the present invention discloses a nickel sulfide nanosheet array co-modified with iron and molybdenum. The material is a nickel sulfide nanosheet array co-modified with iron and molybdenum grown on a nickel foam substrate, wherein the content of iron atoms is 2.45%. ～10.76%, molybdenum atom content is 1.11%～8.99%; nickel sulfide nanosheet array is formed by stacking nanosheets with rough surface, and each nanosheet is assembled by 30-80nm nanoparticles.
本发明实施例还公布了铁和钼共同修饰的硫化镍纳米片阵列的制备方法，该方法的步骤如下：The embodiment of the present invention also discloses a method for preparing nickel sulfide nanosheet arrays co-modified by iron and molybdenum. The steps of the method are as follows:
(1)将清洗干净的泡沫镍置于60mL含有0.05mol/L Ni(NO3)2·6H2O、0.167mol/L尿素和0.067mol/L氟化铵的澄清溶液中，利用溶剂热法在120℃的条件下反应6h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的氢氧化镍纳米片阵列。(1) Place the cleaned nickel foam in 60mL of a clear solution containing 0.05mol/L Ni(NO3 )2 6H2 O, 0.167mol/L urea and 0.067mol/L ammonium fluoride, and use solvothermal method The reaction was carried out at 120°C for 6h. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel hydroxide nanosheet array grown on the nickel foam.
(2)利用第二次水热方法将氢氧化镍转化为硫化镍，同时将Fe、Mo原子引入。依次将0.06mol/L硫脲、0.07mol/L Fe2(SO4)3和0.03mol/L K2MoO4溶解于60mL的去离子水中，并搅拌反应约30min。将氢氧化镍纳米片阵列置于该澄清溶液中，利用溶剂热法在120℃的条件下反应14h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的铁和钼共同修饰的硫化镍纳米片阵列。(2) Using the second hydrothermal method to convert nickel hydroxide into nickel sulfide, while introducing Fe and Mo atoms. 0.06 mol/L thiourea, 0.07 mol/L Fe2 (SO4)3 and 0.03 mol/L K2 MoO4 were dissolved in 60 mL of deionized water in sequence, and stirred for about 30 min. The nickel hydroxide nanosheet array was placed in the clear solution, and reacted at 120° C. for 14 h by solvothermal method. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel sulfide nanosheet array co-decorated with iron and molybdenum grown on the nickel foam.
(3)将制备得到的铁和钼共同修饰的硫化镍纳米片阵列作为工作电极、氧化汞电极为参比电极、石墨棒电极为对电极构成三电极体系置于碱性水和海水溶液中测试其海水氧化性能。该样品在10、100和500mA cm-2的电流密度时海水氧化的过电势如表1所示。(3) The prepared nickel sulfide nanosheet array co-modified with iron and molybdenum was used as the working electrode, the mercury oxide electrode was used as the reference electrode, and the graphite rod electrode was used as the counter electrode to form a three-electrode system, which was tested in alkaline water and seawater solution. Its seawater oxidation properties. Table 1 shows the overpotentials of seawater oxidation for this sample at current densities of 10, 100 and 500 mA cm-2 .
实施例5Example 5
本发明实施例公布了一种铁和钼共同修饰的硫化镍纳米片阵列，该材料为生长在泡沫镍基底上的铁和钼共同修饰的硫化镍纳米片阵列，其中，铁原子含量为2.45％～10.76％，钼原子含量为1.11％～8.99％；硫化镍纳米片阵列由表面粗糙的纳米片堆积而成，且每个纳米片由30-80nm的纳米颗粒组装而成。The embodiment of the present invention discloses a nickel sulfide nanosheet array co-modified with iron and molybdenum. The material is a nickel sulfide nanosheet array co-modified with iron and molybdenum grown on a nickel foam substrate, wherein the content of iron atoms is 2.45%. ～10.76%, molybdenum atom content is 1.11%～8.99%; nickel sulfide nanosheet array is formed by stacking nanosheets with rough surface, and each nanosheet is assembled by 30-80nm nanoparticles.
本发明实施例还公布了铁和钼共同修饰的硫化镍纳米片阵列的制备方法，该方法的步骤如下：The embodiment of the present invention also discloses a method for preparing nickel sulfide nanosheet arrays co-modified by iron and molybdenum. The steps of the method are as follows:
(1)将清洗干净的泡沫镍置于60mL含有0.05mol/L Ni(NO3)2·6H2O、0.167mol/L尿素和0.067mol/L氟化铵的澄清溶液中，利用溶剂热法在120℃的条件下反应6h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的氢氧化镍纳米片阵列。(1) Place the cleaned nickel foam in 60mL of a clear solution containing 0.05mol/L Ni(NO3 )2 6H2 O, 0.167mol/L urea and 0.067mol/L ammonium fluoride, and use solvothermal method The reaction was carried out at 120°C for 6h. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel hydroxide nanosheet array grown on the nickel foam.
(2)利用第二次水热方法将氢氧化镍转化为硫化镍，同时将Fe、Mo原子引入。依次将0.042mol/L硫脲、0.042mol/L Fe(NO3)2·9H2O和0.02mol/LNa2MoO4·2H2O溶解于60mL的去离子水中，并搅拌反应约30min。将氢氧化镍纳米片阵列置于该澄清溶液中，利用溶剂热法在100℃的条件下反应20h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的铁和钼共同修饰的硫化镍纳米片阵列。(2) Using the second hydrothermal method to convert nickel hydroxide into nickel sulfide, while introducing Fe and Mo atoms. 0.042 mol/L thiourea, 0.042 mol/L Fe(NO3 )2 ·9H2 O and 0.02 mol/L Na2 MoO4 ·2H2 O were dissolved in 60 mL of deionized water in sequence, and the reaction was stirred for about 30 min. The nickel hydroxide nanosheet array was placed in the clear solution, and reacted at 100° C. for 20 h by solvothermal method. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel sulfide nanosheet array co-decorated with iron and molybdenum grown on the nickel foam.
(3)将制备得到的铁和钼共同修饰的硫化镍纳米片阵列作为工作电极、氧化汞电极为参比电极、石墨棒电极为对电极构成三电极体系置于碱性水和海水溶液中测试其海水氧化性能。该样品在10、100和500mA cm-2的电流密度时海水氧化的过电势如表1所示。(3) The prepared nickel sulfide nanosheet array co-modified with iron and molybdenum was used as the working electrode, the mercury oxide electrode was used as the reference electrode, and the graphite rod electrode was used as the counter electrode to form a three-electrode system, which was tested in alkaline water and seawater solution. Its seawater oxidation properties. Table 1 shows the overpotentials of seawater oxidation for this sample at current densities of 10, 100 and 500 mA cm-2 .
实施例6Example 6
本发明实施例公布了一种铁和钼共同修饰的硫化镍纳米片阵列，该材料为生长在泡沫镍基底上的铁和钼共同修饰的硫化镍纳米片阵列，其中，铁原子含量为2.45％～10.76％，钼原子含量为1.11％～8.99％；硫化镍纳米片阵列由表面粗糙的纳米片堆积而成，且每个纳米片由30-80nm的纳米颗粒组装而成。The embodiment of the present invention discloses a nickel sulfide nanosheet array co-modified with iron and molybdenum. The material is a nickel sulfide nanosheet array co-modified with iron and molybdenum grown on a nickel foam substrate, wherein the content of iron atoms is 2.45%. ～10.76%, molybdenum atom content is 1.11%～8.99%; nickel sulfide nanosheet array is formed by stacking nanosheets with rough surface, and each nanosheet is assembled by 30-80nm nanoparticles.
本发明实施例还公布了铁和钼共同修饰的硫化镍纳米片阵列的制备方法，该方法的步骤如下：The embodiment of the present invention also discloses a method for preparing nickel sulfide nanosheet arrays co-modified by iron and molybdenum. The steps of the method are as follows:
(1)将清洗干净的泡沫镍置于60mL含有0.05mol/L Ni(NO3)2·6H2O、0.167mol/L尿素和0.067mol/L氟化铵的澄清溶液中，利用溶剂热法在120℃的条件下反应6h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的氢氧化镍纳米片阵列。(1) Place the cleaned nickel foam in 60mL of a clear solution containing 0.05mol/L Ni(NO3 )2 6H2 O, 0.167mol/L urea and 0.067mol/L ammonium fluoride, and use solvothermal method The reaction was carried out at 120°C for 6h. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel hydroxide nanosheet array grown on the nickel foam.
(2)利用第二次水热方法将氢氧化镍转化为硫化镍，同时将Fe、Mo原子引入；依次将0.1mol/L硫脲、0.1mol/L Fe2(SO4)3和0.08mol/LNa2MoO4·2H2O溶解于60mL的去离子水中，并搅拌反应约30min。将氢氧化镍纳米片阵列置于该澄清溶液中，利用溶剂热法在100℃的条件下反应20h。反应完成并冷却至室温后，冲洗干净后在烘箱中烘干，得到生长在泡沫镍上的铁和钼共同修饰的硫化镍纳米片阵列。(2) Use the second hydrothermal method to convert nickel hydroxide into nickel sulfide, and at the same time introduce Fe and Mo atoms; sequentially introduce 0.1mol/L thiourea, 0.1mol/L Fe2 (SO4)3 and 0.08mol/L LNa2 MoO4 ·2H2 O was dissolved in 60 mL of deionized water, and stirred for about 30 min. The nickel hydroxide nanosheet array was placed in the clear solution, and reacted at 100° C. for 20 h by solvothermal method. After the reaction is completed and cooled to room temperature, it is rinsed and dried in an oven to obtain a nickel sulfide nanosheet array co-decorated with iron and molybdenum grown on the nickel foam.
(3)将制备得到的铁和钼共同修饰的硫化镍纳米片阵列作为工作电极、氧化汞电极为参比电极、石墨棒电极为对电极构成三电极体系置于碱性水和海水溶液中测试其海水氧化性能。该样品在10、100和500mA cm-2的电流密度时海水氧化的过电势如表1所示。(3) The prepared nickel sulfide nanosheet array co-modified with iron and molybdenum was used as the working electrode, the mercury oxide electrode was used as the reference electrode, and the graphite rod electrode was used as the counter electrode to form a three-electrode system, which was tested in alkaline water and seawater solution. Its seawater oxidation properties. Table 1 shows the overpotentials of seawater oxidation for this sample at current densities of 10, 100 and 500 mA cm-2 .
表1不同实施例制备得到的FeMo-Ni3S2样品的海水氧化性能汇总表Table 1 Summary of Seawater Oxidation Performance of FeMo-Ni3 S2 Samples Prepared by Different Examples
以上所述，仅为本公开的具体实施方式，但本公开的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本公开揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本公开的保护范围之内。因此，本公开的保护范围应以权利要求的保护范围为准。The above is only a specific implementation of the present disclosure, but the scope of protection of the present disclosure is not limited thereto. Anyone skilled in the art can easily think of changes or substitutions within the technical scope of the present disclosure. should fall within the protection scope of the present disclosure. Therefore, the protection scope of the present disclosure should be determined by the protection scope of the claims.
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