CN112090426A - Metal metastable phase electrolyzed water oxygen evolution catalyst and preparation method and application thereof - Google Patents

Metal metastable phase electrolyzed water oxygen evolution catalyst and preparation method and application thereof Download PDF

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CN112090426A
CN112090426A CN202010922094.3A CN202010922094A CN112090426A CN 112090426 A CN112090426 A CN 112090426A CN 202010922094 A CN202010922094 A CN 202010922094A CN 112090426 A CN112090426 A CN 112090426A
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安长华
闫文秀
安超
申勇立
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Abstract

本发明提供一种金属亚稳相电催化材料制备方法及其应用，所述催化剂为超薄多孔六方镍纳米片，其表面有FeOx团簇修饰和大量的镍空位，所得到的新型催化剂表达式为FeOx@hcpNi。本发明通过常温甲烷Plasma处理铁掺杂的六方相氢氧化镍超薄的纳米片，原位拓扑转化为FeOx团簇修饰的超薄多孔六方镍纳米片。该催化剂在电催化产氧中表现出超低的过电位和优异的稳定性，并且制备过程简单，成本低廉，重复性高，方便生产，为亚稳相金属催化剂合成提供了一条新方法，也为新能源材料的开发利用提供了一条新思路。

Figure 202010922094

The invention provides a preparation method and application of a metal metastable phase electrocatalytic material. The catalyst is an ultra-thin porous hexagonal nickel nanosheet whose surface is decorated with FeOx clusters and a large number of nickel vacancies. is FeOx@hcpNi. In the invention, the iron-doped hexagonal nickel hydroxide ultrathin nanosheets are treated with methane Plasma at room temperature, and the in-situ topological transformation is converted into ultrathin porous hexagonal nickel nanosheets modified by FeOx clusters. The catalyst exhibits ultra-low overpotential and excellent stability in electrocatalytic oxygen production, and the preparation process is simple, low in cost, high in repeatability and convenient in production, which provides a new method for the synthesis of metastable metal catalysts. It provides a new idea for the development and utilization of new energy materials.

Figure 202010922094

Description

一种金属亚稳相电解水析氧催化剂及其制备方法和应用A kind of metal metastable phase electrolysis water oxygen evolution catalyst and preparation method and application thereof

技术领域technical field

本发明属于催化材料技术领域，具体地说，涉及一种金属亚稳相电解水析氧催化剂及其制备方法和应用，更为具体的，是一种应用于电催化水产氧FeOx团簇修饰的超薄多孔六方镍纳米片催化剂。The invention belongs to the technical field of catalytic materials, and in particular relates to a metal metastable phase electrolysis water oxygen evolution catalyst, a preparation method and application thereof, and more specifically, a metal metastable phase electrolysis water oxygen evolution catalyst and FeOx cluster modification applied to electrocatalytic water oxygen production. Ultrathin porous hexagonal nickel nanosheet catalysts.

背景技术Background technique

随着社会经济和人类社会的发展，传统化石燃料的消耗和能源需求的增加成为一个具有挑战性的问题。能源利用过程中产生的环境问题导致了新型绿色能源催化剂的发展。电化学电解水在阴极上产生氢，在阳极上产生氧，是一种很有前途的策略。即把间歇的可再生能源，如阳光、风能和水力，转化为可储存的化学燃料。在这个过程中，阳极氧化反应(OER)是关键步骤，其涉及四电子步骤与低迟缓动力学。提高反应效率的关键是寻找合适的催化剂来加速相应的反应速率。贵金属氧化物如IrO2或RuO2常被用作OER催化剂的基准，在10mA cm-2时过电位为350mV。然而，由于资源稀缺、成本较高，阻碍了其进一步的应用。因此，开发廉价、高效、稳定的非贵金属电解水催化剂显得尤为重要。实现活性电催化剂的晶相控制为优化OER提供了一条新的途径。然而，合成亚稳晶相的过渡金属电催化剂不是很容易，高效的体系的组装也具有挑战性。With the development of social economy and human society, the consumption of traditional fossil fuels and the increase in energy demand have become a challenging problem. Environmental concerns arising from energy utilization have led to the development of new green energy catalysts. Electrochemical water electrolysis, which produces hydrogen at the cathode and oxygen at the anode, is a promising strategy. That is, converting intermittent renewable energy sources, such as sunlight, wind and water, into storable chemical fuels. In this process, the anodic oxidation reaction (OER) is a key step, which involves a four-electron step with low sluggish kinetics. The key to improving the reaction efficiency is to find suitable catalysts to accelerate the corresponding reaction rate. Noble metal oxides such as IrO2 or RuO2 are often used as benchmarks for OER catalysts with an overpotential of 350mV at 10mA cm -2 . However, the scarcity of resources and high cost hinder its further application. Therefore, it is particularly important to develop inexpensive, efficient and stable non-precious metal catalysts for water electrolysis. Achieving crystal phase control of active electrocatalysts provides a new avenue for optimizing OER. However, the synthesis of metastable crystalline phase transition metal electrocatalysts is not easy, and the assembly of efficient systems is challenging.

Ni基催化涉及各个领域，特别是NiFe合金由于其低成本和固有的催化活性成为了最具前景可替代贵金属的电解水催化剂。而六方(hcp)相具有比fcc相更高的反应活性。在hcp Ni多孔纳米片表面组装FeOx团簇和产生的大量镍空位，可有效提强电催化产氧性能。此类电催化析氧催化剂研究未见报道。Ni-based catalysis involves various fields, especially NiFe alloys have become the most promising water electrolysis catalysts to replace noble metals due to their low cost and inherent catalytic activity. The hexagonal (hcp) phase has higher reactivity than the fcc phase. The assembly of FeOx clusters and a large number of nickel vacancies on the surface of hcp Ni porous nanosheets can effectively enhance the electrocatalytic oxygen production performance. Such electrocatalytic oxygen evolution catalyst research has not been reported.

发明内容SUMMARY OF THE INVENTION

本发明提供一种金属亚稳相电解水析氧催化剂及其制备方法和应用，该催化剂在电催化产氧测试中表现出较低的过电位和优异的稳定性，为亚稳相合成提供了一条新方法，从而为新能源材料的开发利用提供了一条新思路。The invention provides a metal metastable phase electrolysis water oxygen evolution catalyst, a preparation method and application thereof. The catalyst exhibits low overpotential and excellent stability in an electrocatalytic oxygen generation test, and provides a catalyst for metastable phase synthesis. A new method, thus providing a new idea for the development and utilization of new energy materials.

为解决上述技术问题，本发明采用以下技术方案予以实现：In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions to be realized:

本发明提供一种新型电催化产氧催化剂的制备方法和应用。该催化剂首先通过水热方法一步直接合成铁掺杂的六方相氢氧化镍超薄的纳米片，然后通过常温甲烷Plasma处理，原位拓扑转化为FeOx团簇修饰的超薄多孔六方镍纳米片。所述方法具有成本低廉，重复性好，节能环保的优点，能够制备性能显著提高的电催化产氧的催化剂。The invention provides a preparation method and application of a novel electrocatalytic oxygen generating catalyst. The catalyst firstly synthesized Fe-doped hexagonal nickel hydroxide ultrathin nanosheets directly by one-step hydrothermal method, and then by room temperature methane Plasma treatment, in situ topological transformation into ultrathin porous hexagonal nickel nanosheets decorated with FeOx clusters. The method has the advantages of low cost, good repeatability, energy saving and environmental protection, and can prepare a catalyst for electrocatalytic oxygen production with significantly improved performance.

一种金属亚稳相电解水析氧催化剂，所述催化剂为超薄多孔六方镍纳米片，其表面有FeOx团簇修饰和大量的镍空位，有效提强电催化产氧性能，所得到的新型催化剂表达式为FeOx@hcp Ni。所述电催化剂为一种应用于电催化水产氧FeOx团簇修饰的超薄多孔六方镍纳米片催化剂。A metal metastable phase electrolysis water oxygen evolution catalyst, the catalyst is an ultra-thin porous hexagonal nickel nanosheet, and its surface is decorated with FeOx clusters and a large number of nickel vacancies, which can effectively improve the electrocatalytic oxygen production performance. The catalyst expression is FeOx@hcp Ni. The electrocatalyst is an ultra-thin porous hexagonal nickel nano-sheet catalyst applied to the modification of FeOx clusters for electrocatalytic oxygen production.

上述金属亚稳相电解水析氧催化剂的制备方法，制备步骤如下：The preparation method of the above-mentioned metal metastable phase electrolysis water oxygen evolution catalyst, the preparation steps are as follows:

(1)采用一步水热方法合成前驱体Fe-Ni(OH)2超薄复合纳米片；(1) A one-step hydrothermal method was used to synthesize the precursor Fe-Ni(OH) 2 ultrathin composite nanosheets;

(2)采用常温甲烷等离子体的方法合成FeOx@hcp Ni超薄多孔纳米片。(2) FeOx@hcp Ni ultrathin porous nanosheets were synthesized by the method of room temperature methane plasma.

具体操作步骤如下：The specific operation steps are as follows:

(1)Fe掺杂Ni(OH)2纳米薄片的合成：采用一步水热法合成了铁掺杂的氢氧化镍，将0.248g Ni(Ac)2·4H2O、0.015g FeCl3·6H2O和0.24g尿素依次加入到蒸馏水中，搅拌溶解后，将得到的混合物转移到聚四氟乙烯的不锈钢高压釜中，150-200℃反应6-10h，然后用水和乙醇洗涤三次后离心收集，置于30-60℃真空干燥箱干燥10-20h，得到Fe-Ni(OH)2前驱体；(1) Synthesis of Fe- doped Ni(OH) 2 nanosheets: Fe - doped nickel hydroxide was synthesized by one - step hydrothermal method. 2 O and 0.24g urea were added to distilled water in turn, and after stirring and dissolving, the obtained mixture was transferred to a stainless steel autoclave of polytetrafluoroethylene, reacted at 150-200°C for 6-10h, then washed with water and ethanol for three times and collected by centrifugation , placed in a vacuum drying oven at 30-60°C for 10-20h to obtain Fe-Ni(OH) 2 precursor;

(2)FeOx@hcp Ni多孔超薄纳米片的合成：将覆盖Fe-Ni(OH)2的石英板材放置在等离子体化学气相沉积(PECVD)***的反应室中，稳定在20-30Pa，室温下用CH4等离子体处理数分钟；反应完成后，样品颜色由黄绿色变为黑色，用上述方法可以得到hcp Ni多孔超薄纳米片。(2) Synthesis of FeOx@hcp Ni porous ultrathin nanosheets: The Fe-Ni(OH) 2 -covered quartz plate was placed in the reaction chamber of a plasma chemical vapor deposition (PECVD) system, stabilized at 20-30Pa at room temperature After the reaction is completed, the color of the sample changes from yellow-green to black, and the above - mentioned method can be used to obtain hcp Ni porous ultrathin nanosheets.

上述金属亚稳相电解水析氧催化剂在电催化产氧方面的应用。The application of the above metal metastable phase electrolysis water oxygen evolution catalyst in electrocatalytic oxygen generation.

二、新型纳米电催化剂FeOx@hcp Ni超薄多孔纳米片的电催化析氧性能研究，方法如下：2. Study on the electrocatalytic oxygen evolution performance of the new nano-electrocatalyst FeOx@hcp Ni ultra-thin porous nanosheets. The methods are as follows:

称取3-5mg催化剂，将其放入50μL加有5％Nafion(8％v/v)的乙醇(92％v/v)溶液中，超声30min，然后将其全部涂加到1cm×1cm的碳纸上，自然干燥后用作工作电极。碳棒作为对电极，Hg/HgO电极为参比电极，在三电极体系中研究OER活性，所有电化学测试均在CHI760E电化学工作站进行，以饱和O2的1M KOH(pH＝14)为电解液。所有电位采用可逆性氢电极进行了修正。Weigh 3-5 mg of catalyst, put it into 50 μL of ethanol (92% v/v) solution with 5% Nafion (8% v/v), sonicate for 30 min, and then add it all to a 1cm×1cm On carbon paper, it was used as working electrode after natural drying. The carbon rod was used as the counter electrode, and the Hg/HgO electrode was used as the reference electrode. The OER activity was investigated in a three-electrode system. All electrochemical tests were carried out on a CHI760E electrochemical workstation, using 1 M KOH (pH=14) saturated with O as the electrolytic liquid. All potentials were corrected using reversible hydrogen electrodes.

本发明制备的催化剂在电催化产氧中表现出超低的过电位和优异的稳定性，并且制备过程简单，成本低廉，重复性高，方便生产，为亚稳相金属催化剂合成提供了一条新方法，也为新能源材料的开发利用提供了一条新思路。The catalyst prepared by the invention shows ultra-low overpotential and excellent stability in electrocatalytic oxygen production, and has the advantages of simple preparation process, low cost, high repeatability and convenient production, and provides a new method for the synthesis of metastable phase metal catalysts. The method also provides a new idea for the development and utilization of new energy materials.

附图说明Description of drawings

图1为实施例1-2制备催化剂的扫描电镜(SEM)照片：其中图(a)和图(b)-分别为Fe@Ni(OH)2和FeOx@hcp Ni，plasma处理样品表面有明显的的孔洞出现，改变了原始的Fe@Ni(OH)2的表面结构。Figure 1 is a scanning electron microscope (SEM) photo of the catalyst prepared in Example 1-2: Figures (a) and (b) - are Fe@Ni(OH) 2 and FeOx@hcp Ni, respectively, and the plasma treated samples have obvious surface The pores appear, which changes the surface structure of the pristine Fe@Ni(OH) 2 .

图2为实施例2制备催化剂的透射电镜(TEM)照片；其中图(a)为FeOx@hcp Ni的衍射环，说明制备的FeOx@hcp Ni为多晶。图(b)为低倍透射电镜图，可以看出明显的多孔纳米片结构。Figure 2 is a transmission electron microscope (TEM) photograph of the catalyst prepared in Example 2; Figure (a) is the diffraction ring of FeOx@hcp Ni, indicating that the prepared FeOx@hcp Ni is polycrystalline. Figure (b) is a low magnification transmission electron microscope image, and the obvious porous nanosheet structure can be seen.

图3为本发明制备的FeOx@hcp Ni和hcp Ni的XRD图，表明掺入铁再经plasma处理后的样品，物相没有发生改变，为六方晶相，结晶性有所降低。Figure 3 is the XRD pattern of FeOx@hcp Ni and hcp Ni prepared by the present invention, which shows that the phase of FeOx@hcp Ni and hcp Ni is not changed after doped with iron and then the sample is treated with plasma.

图4为本发明制备的FeOx@hcp Ni和标准样品对比的同步辐射(XAS)图和程序升温还原(H2-TPR图)。图(a)可看出，Fe在催化剂的价态为接近Fe(III)，图(b)中可看出，在FeOx@hcp Ni中并没有发现Fe-Fe键的存在，而通过(c)图，EXAFS模拟得出，FeOx@hcp Ni中Fe以Fe-O键和Fe-Ni键存在。(d)图H2-TPR显示出FeOx@hcp Ni可以被还原，且还原温度均向低温方向移动，进一步证明Fe是以团簇形式存在的。Fig. 4 is the synchrotron radiation (XAS) image and temperature programmed reduction (H 2 -TPR image) of FeOx@hcp Ni prepared by the present invention compared with the standard sample. It can be seen from Figure (a) that the valence state of Fe in the catalyst is close to Fe(III), and from Figure (b), it can be seen that the Fe-Fe bond is not found in FeOx@hcp Ni, but through (c) ) figure, EXAFS simulation shows that Fe in FeOx@hcp Ni exists as Fe-O bond and Fe-Ni bond. (d) Figure H 2 -TPR shows that FeOx@hcp Ni can be reduced, and the reduction temperature is shifted to low temperature, which further proves that Fe exists in the form of clusters.

图5为本发明制备的FeOx@hcp Ni和hcp Ni、Ni(OH)2催化剂的产氧性能比较图。图(a)极化曲线可知经plasma处理后的催化剂，在相同电流密度下，具有更低的过电位，具有更好的产氧性能。而FeOx团簇修饰的超薄多孔六方镍纳米片具有最佳的产氧性能和稳定性。Figure 5 is a graph showing the comparison of oxygen production performance of FeOx@hcp Ni and hcp Ni, Ni(OH) 2 catalysts prepared in the present invention. Figure (a) polarization curve shows that the catalyst treated with plasma has lower overpotential and better oxygen production performance under the same current density. The ultrathin porous hexagonal nickel nanosheets decorated with FeOx clusters have the best oxygen generation performance and stability.

图6是本发明所述金属亚稳相电解水析氧催化剂的制备方法的流程示意图。FIG. 6 is a schematic flowchart of the preparation method of the metal metastable phase electrolysis water oxygen evolution catalyst according to the present invention.

具体实施方式Detailed ways

本发明针对现有合成方法的问题和不足，提供了一种新颖的FeOx团簇修饰的超薄多孔六方镍纳米片电催化剂的制备技术。Aiming at the problems and deficiencies of the existing synthesis methods, the invention provides a novel preparation technology of an ultra-thin porous hexagonal nickel nanosheet electrocatalyst modified by FeOx clusters.

本发明提供了新型电催化剂的合成方法，包括以下步骤：The invention provides a method for synthesizing a novel electrocatalyst, comprising the following steps:

(1)Fe掺杂Ni(OH)2超薄纳米片的合成：采用水热一步法合成了铁掺杂的氢氧化镍：将0.248gNi(Ac)2·4H2O、0.015g FeCl3·6H2O和0.24g尿素依次加入到蒸馏水中，搅拌溶解后，将得到的混合物转移到聚四氟乙烯的不锈钢高压釜中，150℃反应6-10h，然后用水和乙醇洗涤三次后离心收集，置于30-60℃真空干燥箱干燥10-20h，得到Fe-Ni(OH)2前驱体；(1) Synthesis of Fe-doped Ni(OH) 2 ultrathin nanosheets: Fe-doped nickel hydroxide was synthesized by hydrothermal one-step method: 0.248g Ni(Ac) 2 ·4H 2 O, 0.015g FeCl 3 · 6H 2 O and 0.24g urea were added to distilled water in turn, and after stirring and dissolving, the obtained mixture was transferred to a stainless steel autoclave made of polytetrafluoroethylene, reacted at 150°C for 6-10h, washed three times with water and ethanol, and collected by centrifugation. Place in a vacuum drying oven at 30-60°C for 10-20h to obtain Fe-Ni(OH) 2 precursor;

(2)FeOx@hcp Ni超薄多孔纳米片的合成：将覆盖了Fe-Ni(OH)2的石英石板材放置在等离子体化学气相沉积(PECVD)***的反应室中，然后稳定在20-30Pa，室温下用CH4等离子体处理数分钟，反应完成后，样品颜色由黄绿色变为黑色，用上述的方法得到了hcp Ni超薄多孔纳米片(2) Synthesis of FeOx@hcp Ni ultrathin porous nanosheets: Fe-Ni(OH) 2 -coated quartz stone sheets were placed in the reaction chamber of a plasma chemical vapor deposition (PECVD) system, and then stabilized at 20- 30Pa, treated with CH4 plasma for several minutes at room temperature, after the reaction was completed, the color of the sample changed from yellow-green to black, and the hcp Ni ultra-thin porous nanosheets were obtained by the above method

新型纳米电催化剂FeOx@hcp Ni超薄多孔纳米片的电催化析氧性能研究，方法如下：The electrocatalytic oxygen evolution performance of the new nano-electrocatalyst FeOx@hcp Ni ultra-thin porous nanosheets was studied as follows:

称取5mg电催化剂，将其放入50μL加有5％Nafion(8％v/v)的乙醇(92％v/v)溶液里，超声分散30min，然后将其全部滴凃到1cm×1cm的碳纸上，自然干燥后用作工作电极。碳棒作为对电极，Hg/HgO电极为参比电极，在三电极体系中研究催化剂的OER活性，所有电化学测试均通过CHI 760E电化学工作站在饱和O2的1M KOH(pH＝14)电解液中进行。所有的电位都用可逆性氢电极进行了修正。Weigh 5 mg of electrocatalyst, put it into 50 μL of ethanol (92% v/v) solution with 5% Nafion (8% v/v), ultrasonically disperse it for 30 min, and then drop it all onto a 1cm×1cm surface. On carbon paper, it was used as working electrode after natural drying. A carbon rod was used as the counter electrode, and the Hg/HgO electrode was used as the reference electrode. The OER activity of the catalyst was investigated in a three-electrode system, and all electrochemical tests were performed by CHI 760E electrochemical workstation in 1M KOH (pH=14) saturated with O2 . carried out in liquid. All potentials were corrected with reversible hydrogen electrodes.

下面结合附图和具体实施方式对本发明作进一步详细说明。The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

实施例1Example 1

具有电催化产氧的催化剂Fe-Ni(OH)2超薄纳米片的制备与性能测试。Preparation and performance testing of Fe-Ni(OH) 2 ultrathin nanosheets as a catalyst with electrocatalytic oxygen production.

(1)Fe掺杂Ni(OH)2纳米薄片的合成：采用水热一步法合成了铁掺杂的氢氧化镍。简单地说，将0.248g Ni(Ac)2·4H2O、0.015g FeCl3·6H2O和0.24g尿素依次加入到蒸馏水中。搅拌溶解后，将得到的混合物转移到聚四氟乙烯的不锈钢高压釜中，150-200℃反应6h，然后用水和乙醇洗涤三次后离心收集，置于30-60℃真空干燥箱干燥10-20h，得到Fe-Ni(OH)2前驱体。(1) Synthesis of Fe-doped Ni(OH) 2 nanoflakes: Fe-doped nickel hydroxide was synthesized by a hydrothermal one-step method. Briefly, 0.248 g Ni(Ac) 2 ·4H 2 O, 0.015 g FeCl 3 ·6H 2 O and 0.24 g urea were sequentially added to distilled water. After stirring and dissolving, the obtained mixture was transferred to a stainless steel autoclave made of polytetrafluoroethylene, reacted at 150-200 °C for 6 h, washed with water and ethanol for three times, collected by centrifugation, and placed in a vacuum drying oven at 30-60 °C for 10-20 h. , the Fe-Ni(OH) 2 precursor was obtained.

(2)称取5mg电催化剂，将其放入50μL加有5％Nafion(8％v/v)的乙醇(92％v/v)溶液里，超声分散30min，然后将其全部滴涂到1cm×1cm的碳纸上，自然干燥后用作工作电极。碳棒作为对电极，Hg/HgO电极为参比电极，在三电极体系中研究催化剂的OER活性，所有电化学实验均通过CHI 760E电化学工作站在饱和O2的1M KOH(pH＝14)电解液中进行。所有的电位都用可逆性氢电极进行了修正。(2) Weigh 5 mg of electrocatalyst, put it into 50 μL of ethanol (92% v/v) solution with 5% Nafion (8% v/v), ultrasonically disperse it for 30 min, and then drop it all to 1 cm On the carbon paper of ×1 cm, it was used as the working electrode after natural drying. A carbon rod was used as the counter electrode, and the Hg/HgO electrode was used as the reference electrode. The OER activity of the catalysts was investigated in a three-electrode system. All electrochemical experiments were performed by a CHI 760E electrochemical workstation in 1 M KOH (pH=14) saturated with O 2 . carried out in liquid. All potentials were corrected with reversible hydrogen electrodes.

实施例2Example 2

具有优异电催化产氧电催化剂FeOx@hcp Ni超薄多孔纳米片的制备与性能测试。Preparation and performance testing of ultrathin porous nanosheets of FeOx@hcp Ni with excellent electrocatalytic oxygen production.

(1)FeOx@hcp Ni超薄多孔纳米片的合成：将覆盖了Fe-Ni(OH)2的石英板材放置在等离子体化学气相沉积(PECVD)***的反应室中，然后稳定在20-30Pa，室温下用CH4等离子体处理数分钟。反应完成后，样品颜色由黄绿色变为黑色。用类似的方法得到了hcp Ni超薄多孔纳米片(1) Synthesis of FeOx@hcp Ni ultrathin porous nanosheets: Fe-Ni(OH) 2 -covered quartz plates were placed in the reaction chamber of a plasma chemical vapor deposition (PECVD) system, and then stabilized at 20-30Pa , treated with CH plasma for several minutes at room temperature . After the reaction was completed, the color of the sample changed from yellow-green to black. hcp Ni ultrathin porous nanosheets were obtained by a similar method

(2)新型纳米电催化剂FeOx@hcp Ni超薄多孔纳米片的电催化析氧性能研究，方法如下：称取5mg电催化剂，将其放入50μL加有5％Nafion(8％v/v)的乙醇(92％v/v)溶液里，超声分散30min，然后将其全部滴涂到1cm×1cm的碳纸上，自然干燥后用作工作电极。碳棒作为对电极，Hg/HgO电极为参比电极，在三电极体系中研究催化剂的OER活性，所有电化学实验均通过CHI 760E电化学工作站在饱和O2的1M KOH(pH＝14)电解液中进行。所有的电位都用可逆性氢电极进行了修正。(2) Study on the electrocatalytic oxygen evolution performance of the new nano-electrocatalyst FeOx@hcp Ni ultra-thin porous nanosheets, the method is as follows: Weigh 5 mg of electrocatalyst, put it into 50 μL with 5% Nafion (8% v/v) In ethanol (92% v/v) solution, ultrasonically dispersed for 30 min, and then all of it was drop-coated on 1 cm × 1 cm carbon paper, and it was used as a working electrode after natural drying. A carbon rod was used as the counter electrode, and the Hg/HgO electrode was used as the reference electrode. The OER activity of the catalysts was investigated in a three-electrode system. All electrochemical experiments were performed by a CHI 760E electrochemical workstation in 1 M KOH (pH=14) saturated with O 2 . carried out in liquid. All potentials were corrected with reversible hydrogen electrodes.

为了证明本催化剂物相及表面结构组成，对其进行了SEM、TEM、XRD、XPS、XAES、H2-TPR表征。对催化剂进行性能测试，以比较本发明制备催化剂对电催化析氧性能的显著提高。对该催化剂进行长达20h稳定性测试，以证明本催化剂的稳定性。In order to prove the phase and surface structure of the catalyst, SEM, TEM, XRD, XPS, XAES, H 2 -TPR were carried out to characterize the catalyst. The performance test of the catalyst is carried out to compare the remarkable improvement of the electrocatalytic oxygen evolution performance of the catalyst prepared by the present invention. The catalyst was tested for stability for up to 20 hours to prove the stability of the catalyst.

图1为实施例1-2制备电催化剂的扫描电镜(SEM)照片：其中图(a)和图(b)分别为Fe@Ni(OH)2和FeOx@hcp Ni，plasma处理，样品表面有明显的的孔洞出现，改变了原始的Fe@Ni(OH)2的表面结构。Figure 1 is a scanning electron microscope (SEM) photo of the electrocatalyst prepared in Example 1-2: Figures (a) and (b) are Fe@Ni(OH) 2 and FeOx@hcp Ni, respectively, treated with plasma, and the surface of the sample has Obvious voids appear, changing the surface structure of the pristine Fe@Ni(OH) 2 .

图2为发明实施例2制备的电催化剂的透射电镜(TEM)照片；其中图(a)为FeOx@hcpNi的衍射环，说明制备的FeOx@hcp Ni为多晶。图(b)为低倍的透射电镜图，可以看出明显的多孔结构。Figure 2 is a transmission electron microscope (TEM) photograph of the electrocatalyst prepared in Example 2 of the invention; Figure (a) is the diffraction ring of FeOx@hcpNi, indicating that the prepared FeOx@hcpNi is polycrystalline. Figure (b) is a low magnification transmission electron microscope image, which shows an obvious porous structure.

图3为本发明实施例1-2制备的FeOx@hcp Ni和hcp Ni的XRD图。图中，掺入铁后，再经plasma处理后的样品，物相没有发生改变，为六方晶相，但结晶性有所降低。3 is the XRD pattern of FeOx@hcp Ni and hcp Ni prepared in Example 1-2 of the present invention. In the figure, after doped with iron, the sample after plasma treatment has no change in phase and is a hexagonal crystal phase, but the crystallinity is reduced.

图4为本发明实施例2制备的FeOx@hcp Ni和标准样品对比的同步辐射(XAS)图和程序升温还原(H2-TPR图)。图(a)可看出，Fe在催化剂的价态为Fe(III)，图(b)中可看出，在FeOx@hcp Ni中并没有发现Fe-Fe键的存在，而通过(c)图，EXAFS模拟得出FeOx@hcp Ni中Fe以Fe-O键和Fe-Ni键存在。(d)图H2-TPR显示出FeOx@hcp Ni可以被还原，且还原温度均向低温方向移动，进一步证明Fe是以团簇形式存在的。FIG. 4 is a synchrotron radiation (XAS) image and a temperature-programmed reduction (H2-TPR image) of FeOx@hcp Ni prepared in Example 2 of the present invention compared with a standard sample. As can be seen from Figure (a), the valence state of Fe in the catalyst is Fe(III), and from Figure (b), it can be seen that the Fe-Fe bond is not found in FeOx@hcp Ni, but through (c) Figure, EXAFS simulation shows that Fe in FeOx@hcp Ni exists as Fe-O bond and Fe-Ni bond. (d) Figure H 2 -TPR shows that FeOx@hcp Ni can be reduced, and the reduction temperature is shifted to low temperature, which further proves that Fe exists in the form of clusters.

图5为本发明实施例1-2制备的FeOx@hcp Ni和hcp Ni、Ni(OH)2电催化剂的产氧性能比较图。图(a)极化曲线可知经plasma处理后的催化剂，在相同电流密度下，具有更低的过电位，具有更好的产氧性能。而FeOx团簇修饰的超薄多孔六方镍纳米片具有最佳的产氧性能且具有更好的稳定性。5 is a graph showing the comparison of oxygen production performance of FeOx@hcp Ni and hcp Ni, Ni(OH) 2 electrocatalysts prepared in Examples 1-2 of the present invention. Figure (a) polarization curve shows that the catalyst treated with plasma has lower overpotential and better oxygen production performance under the same current density. The ultrathin porous hexagonal nickel nanosheets decorated with FeOx clusters have the best oxygen generation performance and better stability.

以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in other forms. Any person skilled in the art may use the technical content disclosed above to make changes or modifications to equivalent changes. Example. However, any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solutions of the present invention still belong to the protection scope of the technical solutions of the present invention.

Claims (4)

1.一种金属亚稳相电解水析氧催化剂，其特征在于：所述催化剂为超薄多孔六方镍纳米片，其表面有FeOx团簇修饰和大量的镍空位，所得到的新型催化剂表达式为FeOx@hcpNi。1. a metal metastable phase electrolysis water oxygen evolution catalyst, it is characterized in that: described catalyzer is ultra-thin porous hexagonal nickel nanosheet, and its surface has FeOx cluster decoration and a large amount of nickel vacancies, and the obtained novel catalyst expression is FeOx@hcpNi. 2.根据权利要求1所述金属亚稳相电解水析氧催化剂的制备方法，其特征在于，制备步骤如下：2. the preparation method of metal metastable phase electrolysis water oxygen evolution catalyst according to claim 1, is characterized in that, preparation step is as follows: (1)采用一步水热方法合成前驱体Fe-Ni(OH)2超薄复合纳米片；(1) A one-step hydrothermal method was used to synthesize the precursor Fe-Ni(OH) 2 ultrathin composite nanosheets; (2)采用常温甲烷等离子体的方法合成FeOx@hcp Ni超薄多孔六方镍纳米片。(2) FeOx@hcp Ni ultrathin porous hexagonal nickel nanosheets were synthesized by the method of room temperature methane plasma. 3.根据权利要求2所述的制备方法，其特征在于，具体操作步骤如下：3. preparation method according to claim 2, is characterized in that, concrete operation steps are as follows: (1)Fe掺杂Ni(OH)2纳米薄片的合成：采用一步水热法合成了铁掺杂的氢氧化镍，将0.248g Ni(Ac)2·4H2O、0.015g FeCl3·6H2O和0.24g尿素依次加入到蒸馏水中，搅拌溶解后，将得到的混合物转移到聚四氟乙烯的不锈钢高压釜中，150-200℃反应6-10h，然后用水和乙醇洗涤三次后离心收集，置于30-60℃真空干燥箱干燥10-20h，得到Fe-Ni(OH)2前驱体；(1) Synthesis of Fe- doped Ni(OH) 2 nanosheets: Fe - doped nickel hydroxide was synthesized by one - step hydrothermal method. 2 O and 0.24g urea were added to distilled water in turn, and after stirring and dissolving, the obtained mixture was transferred to a stainless steel autoclave of polytetrafluoroethylene, reacted at 150-200°C for 6-10h, then washed with water and ethanol for three times and collected by centrifugation , placed in a vacuum drying oven at 30-60°C for 10-20h to obtain Fe-Ni(OH) 2 precursor; (2)FeOx@hcp Ni多孔超薄纳米片的合成：将覆盖Fe-Ni(OH)2的石英板材放置在等离子体化学气相沉积(PECVD)***的反应室中，稳定在20-30Pa，室温下用CH4等离子体处理数分钟；反应完成后，样品颜色由黄绿色变为黑色，用上述方法可以得到hcp Ni多孔超薄纳米片。(2) Synthesis of FeOx@hcp Ni porous ultrathin nanosheets: The Fe-Ni(OH) 2 -covered quartz plate was placed in the reaction chamber of a plasma chemical vapor deposition (PECVD) system, stabilized at 20-30Pa at room temperature After the reaction is completed, the color of the sample changes from yellow-green to black, and the above - mentioned method can be used to obtain hcp Ni porous ultrathin nanosheets. 4.权利要求1所述金属亚稳相电解水析氧催化剂在电催化产氧方面的应用。4. the application of the metal metastable phase electrolysis water oxygen evolution catalyst of claim 1 in electrocatalytic oxygen production.
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