CN110813330A - Co-Fe @ FeF catalyst and two-dimensional nano-array synthesis method - Google Patents
Co-Fe @ FeF catalyst and two-dimensional nano-array synthesis method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 12
- 229910020598 Co Fe Inorganic materials 0.000 title claims abstract description 10
- 229910002519 Co-Fe Inorganic materials 0.000 title claims abstract description 10
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 91
- 229910052742 iron Inorganic materials 0.000 claims description 28
- 239000006260 foam Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000011160 research Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910021094 Co(NO3)2-6H2O Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
Description
技术领域technical field
本发明涉及无机化学以及电催化研究领域，具体为一种Co-Fe@FeF催化剂及二维纳米阵列合成方法。The invention relates to the research fields of inorganic chemistry and electrocatalysis, in particular to a Co-Fe@FeF catalyst and a method for synthesizing a two-dimensional nanometer array.
背景技术Background technique
为解决传统化石燃料的过度消耗引起的能源危机和环境污染问题，开发高效、环保的能源转化和储存技术已成为重中之重。电催化氧析出反应(Oxygen EvolutionReaction, OER)是电解水制氢和金属-空气电池等能源储存和转化的核心过程，其反应涉及四个电子的转移，是一个动力学慢反应，需要设计制备高效的催化剂才能降低反应的过电位。以Ru和Ir为代表的贵金属基OER电催化剂具有优异的电催化性能，但其高昂的价格和稀缺的储量阻碍了其工业化应用。第一过渡系金属钴(Co)、镍(Ni)和铁(Fe)元素储量丰富、价格低廉，而且其氧化物或羟基氧化物在碱性条件下显示出不错的OER性能。特别是一些Co、Ni和Fe混金属的羟基化合物二维纳米材料由于具有大的比表面、活性位点完全暴露和优异的电子传导能力，显示出媲美于Ru基、Ir基的贵金属催化剂，被认为是最有前途的OER电催化剂之一。然而，这些催化剂的合成方法多为溶剂热法或高温煅烧法等，需要耗费大量的能量，并且通常需要较长的制备时间和多个步骤，不适合大规模工业化生产。In order to solve the energy crisis and environmental pollution caused by the excessive consumption of traditional fossil fuels, the development of efficient and environmentally friendly energy conversion and storage technologies has become a top priority. Electrocatalytic Oxygen Evolution Reaction (OER) is the core process of energy storage and conversion such as hydrogen production from water electrolysis and metal-air batteries. The reaction involves the transfer of four electrons and is a kinetically slow reaction. The catalyst can reduce the overpotential of the reaction. Noble metal-based OER electrocatalysts represented by Ru and Ir have excellent electrocatalytic performance, but their high price and scarce reserves hinder their industrial application. The first transition series metals cobalt (Co), nickel (Ni) and iron (Fe) are abundant and inexpensive, and their oxides or oxyhydroxides show good OER performance under alkaline conditions. In particular, some Co, Ni and Fe mixed metal hydroxy compound two-dimensional nanomaterials show comparable performance to Ru-based and Ir-based noble metal catalysts due to their large specific surface area, fully exposed active sites and excellent electronic conductivity. considered to be one of the most promising OER electrocatalysts. However, the synthesis methods of these catalysts are mostly solvothermal methods or high-temperature calcination methods, which require a lot of energy, and usually require a long preparation time and multiple steps, which are not suitable for large-scale industrial production.
不仅如此，绝大多数性能优异的OER电催化剂只能在电流密度为10 mA cm–2的条件下工作。但是，工业化所需的电催化剂需要在过电位低于300 mV的情况下，电流密度达到500 mA cm–2以上，并且具有良好的稳定性，目前只有极少数的电极材料满足该要求。为了制备满足工业化需求的OER电极材料，通常通过以下四种途径实现：(1)使用具有高的OER本征催化活性物质；(2)催化活性中心完全暴露于材料的表面；(3)能够对抗高强度的氧化条件；(4)容易吸附底物并快速脱附产物。此外，在OER过程中，催化剂必须粘附在电极基底上，防止在大量氧气析出的条件下脱落。但是，制备能够同时满足上述标准的电极材料是极其困难的。因此，快速、环保地合成电化学活性高、稳定性好、成本低的OER电极材料仍然很具有挑战性。Not only that, the vast majority of OER electrocatalysts with excellent performance can only work at a current density of 10 mA cm -2 . However, electrocatalysts required for industrialization require current densities above 500 mA cm -2 with overpotentials below 300 mV and good stability, and only a few electrode materials currently meet this requirement. In order to prepare OER electrode materials that meet the needs of industrialization, it is usually achieved through the following four ways: (1) using materials with high OER intrinsic catalytic activity; (2) the catalytic active center is completely exposed on the surface of the material; (3) can resist the High-strength oxidative conditions; (4) easy adsorption of substrates and rapid desorption of products. Furthermore, during the OER process, the catalyst must adhere to the electrode substrate and prevent it from falling off under conditions of massive oxygen evolution. However, it is extremely difficult to prepare electrode materials that can simultaneously satisfy the above criteria. Therefore, the rapid and environmentally friendly synthesis of OER electrode materials with high electrochemical activity, good stability, and low cost remains challenging.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种Co-Fe@FeF催化剂及二维纳米阵列合成方法，解决上述背景技术中提出的问题。The purpose of the present invention is to provide a Co-Fe@FeF catalyst and a method for synthesizing a two-dimensional nanoarray to solve the problems raised in the above-mentioned background art.
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Co-Fe@FeF催化剂，包含Co/Fe羟基氧化物和泡沫铁的复合材料，所述Co/Fe羟基氧化物在泡沫铁表面形成无定形态的二维纳米阵列。A Co-Fe@FeF catalyst, comprising a composite of Co/Fe oxyhydroxide and iron foam, the Co/Fe oxyhydroxide forming an amorphous two-dimensional nanoarray on the surface of the iron foam.
一种Co-Fe@FeF催化剂二维纳米阵列合成方法，至少包括所述泡沫铁的预处理：将所述泡沫铁依次浸泡于HCl溶液、乙醇和丙酮中超声处理，之后再用去离子水洗涤，再放置于真空烘箱中干燥，得到表面为灰黑色的Co/Fe羟基氧化物。A method for synthesizing a two-dimensional nanoarray of Co-Fe@FeF catalyst, comprising at least pretreatment of the foamed iron: immersing the foamed iron in HCl solution, ethanol and acetone in sequence for ultrasonic treatment, and then washing with deionized water , and then placed in a vacuum oven to dry to obtain a gray-black Co/Fe oxyhydroxide.
更进一步的，将所述处理好的泡沫铁浸泡在硝酸钴和过氧化氢的混合溶液中，并通过控制浸泡时长调控混金属羟基氧化物二维纳米阵列生长。Further, the treated iron foam is soaked in a mixed solution of cobalt nitrate and hydrogen peroxide, and the growth of the two-dimensional nano-array of mixed metal oxyhydroxide is regulated by controlling the soaking time.
更进一步的，所述混合溶液的比例为Co(NO3)2·6H2O (0.7275 g, 2.5 mmol)和5%H2O2 (25 mL)。Further, the ratio of the mixed solution was Co(NO 3 ) 2 ·6H 2 O (0.7275 g, 2.5 mmol) and 5% H 2 O 2 (25 mL).
更进一步的，所述浸泡时长为1~10分钟。Further, the soaking time is 1-10 minutes.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
本发明制备方法独特且简单，通过泡沫铁浸泡在硝酸钴和过氧化氢的混合溶液中，原位生长得到在泡沫铁表面形成呈二维纳米阵列的无定形Co/Fe羟基氧化物，具有优异的电化学稳定性，在高电流密度下使用寿命长，同时展现出潜在工业应用价值前景。The preparation method of the invention is unique and simple. The foamed iron is soaked in a mixed solution of cobalt nitrate and hydrogen peroxide, and the amorphous Co/Fe oxyhydroxide is formed on the surface of the foamed iron and forms a two-dimensional nano-array by in-situ growth. It has excellent electrochemical stability, long service life at high current density, and shows potential industrial application value prospects.
附图说明Description of drawings
图1为本发明实施例Co+Fe@FeF-5的SEM图（a）、TEM图（b）和电子衍射图（c）；Fig. 1 is the SEM image (a), TEM image (b) and electron diffraction image (c) of Co+Fe@FeF-5 according to the embodiment of the present invention;
图2本发明的工艺流程示意图；Fig. 2 process flow schematic diagram of the present invention;
图3为本发明实施例Co+Fe@FeF-5的Raman光谱；Fig. 3 is the Raman spectrum of the embodiment of the present invention Co+Fe@FeF-5;
图4为本发明实施例Co+Fe@FeF-5的Co 2p的XPS光谱；Fig. 4 is the XPS spectrum of Co 2p of Co+Fe@FeF-5 in the embodiment of the present invention;
图5 为本发明实施例Co+Fe@FeF-5的Fe 2p的XPS光谱；Fig. 5 is the XPS spectrum of Fe 2p of Co+Fe@FeF-5 in the embodiment of the present invention;
图6 为本发明实施例Co+Fe@FeF-5的O 1s的XPS光谱；Fig. 6 is the XPS spectrum of O 1s of Co+Fe@FeF-5 in the embodiment of the present invention;
图7 为本发明FeF、Co-Fe@FeF和RuO2的LSV曲线；Fig. 7 is the LSV curve of FeF, Co-Fe@FeF and RuO2 of the present invention;
图8 为本发明实施例Co-Fe@FeF-5的CC曲线。FIG. 8 is the CC curve of Co-Fe@FeF-5 in the embodiment of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行描述。The technical solutions in the embodiments of the present invention will be described below with reference to the accompanying drawings in the embodiments of the present invention.
参阅图1至图8，本发明所提供的技术方案：Referring to Figure 1 to Figure 8, the technical solutions provided by the present invention:
一、实施例1(Co+Fe@FeF-1)：1. Embodiment 1 (Co+Fe@FeF-1):
（1）处理泡沫铁：首先，将面积S = 3 cm×1 cm的泡沫铁(Fe foam, 简称FeF)依次浸泡于0.1 M HCl溶液、乙醇和丙酮中超声3分钟，之后再用去离子水洗涤三次以除去FeF表面的氧化物和油污，放置于25 oC的真空烘箱中干燥12小时，得到表面为灰黑色的泡沫铁。(1) Treatment of iron foam: First, soak iron foam (FeF for short) with an area of S = 3 cm × 1 cm in 0.1 M HCl solution, ethanol and acetone and ultrasonically for 3 minutes, and then use deionized water. After washing three times to remove oxides and oil stains on the surface of FeF, it was dried in a vacuum oven at 25 oC for 12 hours to obtain a gray-black foamed iron on the surface.
（2）将以上处理好的FeF浸泡在Co(NO3)2·6H2O (0.7275 g, 2.5 mmol)和5% H2O2(25 mL)的溶液中，在室温条件下反应1分钟后，灰褐色泡沫铁表面几乎无变化(所得反应物命名为Co+Fe@FeF-1)。(2) Soak the above-treated FeF in a solution of Co(NO 3 ) 2 6H 2 O (0.7275 g, 2.5 mmol) and 5% H 2 O 2 (25 mL), and react at room temperature for 1 minute After that, the surface of gray-brown iron foam was almost unchanged (the obtained reactant was named Co+Fe@FeF-1).
三、实施例2（Co+Fe@FeF-5）：3. Example 2 (Co+Fe@FeF-5):
（1）处理泡沫铁：首先，将面积S = 3 cm×1 cm的泡沫铁(Fe foam, 简称FeF)依次浸泡于0.1 M HCl溶液、乙醇和丙酮中超声3分钟，之后再用去离子水洗涤三次以除去FeF表面的氧化物和油污，放置于25 oC的真空烘箱中干燥12小时，得到表面为灰黑色的泡沫铁。(1) Treatment of iron foam: First, soak iron foam (FeF for short) with an area of S = 3 cm × 1 cm in 0.1 M HCl solution, ethanol and acetone and ultrasonically for 3 minutes, and then use deionized water. After washing three times to remove oxides and oil stains on the surface of FeF, it was dried in a vacuum oven at 25 oC for 12 hours to obtain a gray-black foamed iron on the surface.
（2）将以上处理好的FeF浸泡在Co(NO3)2·6H2O (0.7275 g, 2.5 mmol)和5% H2O2(25 mL)的溶液中，在室温条件下反应5分钟后，灰黑色泡沫铁表面变成红棕色（所得反应物命名为Co+Fe@FeF-5）。(2) Soak the above-treated FeF in a solution of Co(NO 3 ) 2 6H 2 O (0.7275 g, 2.5 mmol) and 5% H 2 O 2 (25 mL), and react at room temperature for 5 minutes After that, the surface of the gray-black iron foam turned reddish-brown (the resulting reactant was named Co+Fe@FeF-5).
三、实施例3（Co+Fe@FeF-10）：3. Example 3 (Co+Fe@FeF-10):
（1）处理泡沫铁：首先，将面积S = 3 cm×1 cm的泡沫铁(Fe foam, 简称FeF)依次浸泡于0.1 M HCl溶液、乙醇和丙酮中超声3分钟，之后再用去离子水洗涤三次以除去FeF表面的氧化物和油污，放置于25 oC的真空烘箱中干燥12小时，得到表面为灰黑色的泡沫铁。(1) Treatment of iron foam: First, soak iron foam (FeF for short) with an area of S = 3 cm × 1 cm in 0.1 M HCl solution, ethanol and acetone and ultrasonically for 3 minutes, and then use deionized water. After washing three times to remove oxides and oil stains on the surface of FeF, it was dried in a vacuum oven at 25 oC for 12 hours to obtain a gray-black foamed iron on the surface.
（2）将以上处理好的FeF浸泡在Co(NO3)2·6H2O (0.7275 g, 2.5 mmol)和5% H2O2(25 mL)的溶液中，在室温条件下反应10分钟后，灰黑色泡沫铁表面红棕色颜色加深（所得反应物命名为Co+Fe@FeF-10）。(2) Soak the above-treated FeF in a solution of Co(NO 3 ) 2 6H 2 O (0.7275 g, 2.5 mmol) and 5% H 2 O 2 (25 mL), and react at room temperature for 10 minutes After that, the reddish-brown color of the gray-black iron foam surface deepened (the obtained reactant was named Co+Fe@FeF-10).
二、对实施例的观测分析：Second, the observation and analysis of the embodiment:
通过扫描电镜和透射电镜对Co+Fe@FeF-5观测，在泡沫铁表面形成二维纳米阵列，并且产物为无定形态（图1）。Co+Fe@FeF-5 was observed by scanning electron microscopy and transmission electron microscopy, and two-dimensional nanoarrays were formed on the surface of the iron foam, and the product was amorphous (Figure 1).
为了确定产物的结构，通过拉曼（Raman）光谱（图3）测试得出产物中含有Co-O键(450 and 525 cm−1)和Fe-O键(660 cm−1)，初步确定产物为Co/Fe羟基氧化物。In order to determine the structure of the product, the Raman spectrum (Fig. 3) shows that the product contains Co-O bonds (450 and 525 cm −1 ) and Fe-O bonds (660 cm −1 ), and the product is preliminarily determined. For Co/Fe oxyhydroxide.
为了进一步确证产物为Co/Fe羟基氧化物，通过测试产物的X-射线光电子能谱（图4~图6），通过峰的归属得出产物中含有：Co2+和Co3+ (~780.5 eV和~795.5 eV处分别归属为Co 2p3/2和Co 2p1/2的峰，在~787.0 eV和~803.0 eV的卫星峰分别是Co2+和Co3+的特征峰)，Fe2+和Fe3+ (724.5 eV and 726.5 eV分别归属为Fe2+和Fe3+的Fe 2p1/2峰，~711.0 eV和~713.5 eV处分别归属为Fe2+和Fe3+的峰)和O以及OH–(~531.0 eV和~532.5 eV分别归属为O和OH–的特征峰)。结合拉曼光谱和X-射线光电子能谱说明原位生长于泡沫铁表面的二维纳米阵列为无定形的Co/Fe羟基氧化物。In order to further confirm that the product is Co/Fe oxyhydroxide, the X-ray photoelectron spectrum of the product was tested (Figure 4~Figure 6), and it was concluded that the product contained: Co 2+ and Co 3+ (~780.5 The peaks at eV and ~795.5 eV are assigned to Co 2p 3/2 and Co 2p 1/2 , respectively, and the satellite peaks at ~787.0 eV and ~803.0 eV are characteristic peaks of Co 2+ and Co 3+ , respectively), Fe 2 + and Fe 3+ (724.5 eV and 726.5 eV are assigned to Fe 2p 1/2 peaks of Fe 2+ and Fe 3+ , respectively, and ~711.0 eV and ~713.5 eV are assigned to Fe 2+ and Fe 3+ peaks, respectively) and O and OH – (~531.0 eV and ~532.5 eV are assigned to characteristic peaks of O and OH – , respectively). Combined with Raman spectroscopy and X-ray photoelectron spectroscopy, the two-dimensional nanoarrays grown in situ on the surface of iron foam are amorphous Co/Fe oxyhydroxides.
二、电化学测试：2. Electrochemical test:
电化学测试使用上海辰华CHI 660E电化学工作站采集，以饱和Ag/AgCl电极作为参比电极，铂丝作为对电极，工作电极为S = 1cm2的样品，电解液为1 mol/L的KOH溶液。CV和LSV扫描的电压窗口均在0.1~0.6 V，扫速分别为50 mV s−1和5 mV s−1，CC的阳极电流值分别为10 mA、100 mA和500 mA。Electrochemical tests were collected using Shanghai Chenhua CHI 660E electrochemical workstation, with saturated Ag/AgCl electrode as the reference electrode, platinum wire as the counter electrode, the working electrode was the sample of S = 1 cm 2 , and the electrolyte was 1 mol/L KOH solution. The voltage windows of CV and LSV scans were both 0.1~0.6 V, the scan rates were 50 mV s −1 and 5 mV s −1 , respectively, and the anodic current values of CC were 10 mA, 100 mA, and 500 mA, respectively.
转换可逆氢电极(Reversible Hydrogen Electrode，RHE)电位的数学表达式为：The mathematical expression for converting the potential of the Reversible Hydrogen Electrode (RHE) is:
E(RHE) = E(Ag/AgCl) + 0.197 V + 0.059pH –IR u E (RHE) = E (Ag/AgCl) + 0.197 V + 0.059pH – IR u
式中：I为测试的电流，R u为溶液阻抗。In the formula: I is the current tested, R u is the solution impedance.
使用循环伏安法活化样品，当CV曲线重合后对样品进行线性扫描并将LSV转换为RHE，Co+Fe@FeF-5在10 mA cm−2和500 mA cm−2的过电位分别为208 mV和298 mV，优于Co+Fe@FeF-1、Co+ Fe@FeF-10、贵金属RuO2的性能（图7)。The samples were activated by cyclic voltammetry, and the samples were linearly scanned after the CV curves overlapped and the LSV was converted to RHE. The overpotentials of Co+Fe@FeF-5 at 10 mA cm −2 and 500 mA cm −2 were 208 mV and 298 mV, which are superior to those of Co+Fe@FeF-1, Co+Fe@FeF-10, and precious metal RuO 2 (Fig. 7).
依次在10 mA cm−2、100 mA cm−2和500 mA cm−2的电流密度条件下电解60小时电压几乎没有升高，具有优异的电化学稳定性（图8），通过收集氧气量计算得到Co+Fe@FeF-5的电催化OER性能满足工业生产的需要，具有潜在工业应用价值。Under the condition of current densities of 10 mA cm −2 , 100 mA cm −2 and 500 mA cm −2 successively, the electrolysis voltage hardly increased for 60 hours, with excellent electrochemical stability (Fig. 8), calculated by the amount of collected oxygen The obtained electrocatalytic OER performance of Co+Fe@FeF-5 meets the needs of industrial production and has potential industrial application value.
综上所述，本发明通过将泡沫铁浸泡在硝酸钴和过氧化氢的混合溶液中，原位生长得到在泡沫铁表面形成了呈二维纳米阵列的无定形Co/Fe羟基氧化物，具有优异的电化学稳定性，在高电流密度下使用寿命长，同时展现出潜在工业应用价值前景。In summary, the present invention obtains amorphous Co/Fe oxyhydroxide with two-dimensional nano-arrays formed on the surface of the foamed iron by immersing the foamed iron in a mixed solution of cobalt nitrate and hydrogen peroxide, and in-situ growth. Excellent electrochemical stability, long service life at high current density, and potential industrial application value prospects.
以上的展示的仅为本发明较佳实施例而已，当然不能以此来限定本发明的权利范围，以此依靠本发明权利要求所作的同等变化，仍属于本发明所涵盖的范围。The above shows are only the preferred embodiments of the present invention, of course, the scope of the rights of the present invention cannot be limited by this, and the equivalent changes made by relying on the claims of the present invention still belong to the scope covered by the present invention.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113774425A (en) * | 2021-09-18 | 2021-12-10 | 南京晓庄学院 | Preparation method and application of a Ru-modified FeCo@NF electrocatalyst |
| CN114150344A (en) * | 2021-12-23 | 2022-03-08 | 北京中海前沿材料技术有限公司 | Cobalt nitride/iron phosphide self-supporting electrode for water decomposition and preparation method thereof |
| CN114843530A (en) * | 2022-03-29 | 2022-08-02 | 中北大学南通智能光机电研究院 | Preparation method of cobalt-iron/foam iron |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693978A (en) * | 2016-12-30 | 2017-05-24 | 王艳 | Metal oxyhydroxide catalyst, electrode, preparation methods of catalyst and electrode and electrochemical electrolysis unit |
| CN107961793A (en) * | 2017-11-27 | 2018-04-27 | 山西大同大学 | Nickel cobalt oxyhydroxide adulterates the analysis oxygen catalysis material of graphene oxide |
| CN109638303A (en) * | 2018-12-27 | 2019-04-16 | 河北工业大学 | A kind of oxygen evolution reaction FeOOH/Co (OH)2The preparation method of composite electrocatalyst |
| US20190127862A1 (en) * | 2016-04-29 | 2019-05-02 | University Of Kansas | Microwave assisted synthesis of metal oxyhydroxides |
| CN109967080A (en) * | 2019-03-28 | 2019-07-05 | 浙江大学 | Preparation method and application of amorphous (Ni, Fe)OOH thin film electrocatalyst supported on the surface of nickel foam |
-
2019
- 2019-11-14 CN CN201911110257.1A patent/CN110813330A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190127862A1 (en) * | 2016-04-29 | 2019-05-02 | University Of Kansas | Microwave assisted synthesis of metal oxyhydroxides |
| CN106693978A (en) * | 2016-12-30 | 2017-05-24 | 王艳 | Metal oxyhydroxide catalyst, electrode, preparation methods of catalyst and electrode and electrochemical electrolysis unit |
| CN107961793A (en) * | 2017-11-27 | 2018-04-27 | 山西大同大学 | Nickel cobalt oxyhydroxide adulterates the analysis oxygen catalysis material of graphene oxide |
| CN109638303A (en) * | 2018-12-27 | 2019-04-16 | 河北工业大学 | A kind of oxygen evolution reaction FeOOH/Co (OH)2The preparation method of composite electrocatalyst |
| CN109967080A (en) * | 2019-03-28 | 2019-07-05 | 浙江大学 | Preparation method and application of amorphous (Ni, Fe)OOH thin film electrocatalyst supported on the surface of nickel foam |
Non-Patent Citations (1)
| Title |
|---|
| BING SHAO ET AL.: "Rapid growth of amorphous cobalt-iron oxyhydroxide nanosheet arrays onto iron foam: Highly efficient and low-cost catalysts for oxygen evolution", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113774425A (en) * | 2021-09-18 | 2021-12-10 | 南京晓庄学院 | Preparation method and application of a Ru-modified FeCo@NF electrocatalyst |
| CN113774425B (en) * | 2021-09-18 | 2022-04-29 | 南京晓庄学院 | Preparation method and application of a Ru-modified FeCo@NF electrocatalyst |
| CN114150344A (en) * | 2021-12-23 | 2022-03-08 | 北京中海前沿材料技术有限公司 | Cobalt nitride/iron phosphide self-supporting electrode for water decomposition and preparation method thereof |
| CN114843530A (en) * | 2022-03-29 | 2022-08-02 | 中北大学南通智能光机电研究院 | Preparation method of cobalt-iron/foam iron |
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