CN111450851B - Preparation method of sulfur-doped cobalt-based nano oxygen evolution electrocatalyst - Google Patents
Preparation method of sulfur-doped cobalt-based nano oxygen evolution electrocatalyst Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 45
- 239000001301 oxygen Substances 0.000 title claims abstract description 45
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 42
- 239000010941 cobalt Substances 0.000 title claims abstract description 42
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 26
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 238000011161 development Methods 0.000 abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- -1 sulfide ions Chemical class 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000001075 voltammogram 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B01J35/33—Electric or magnetic properties
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Abstract
本发明属于电催化材料领域，具体涉及一种硫掺杂的钴基纳米析氧电催化剂的制备方法。所述电催化剂是由钴基硫化物掺杂四氧化三钴纳米立方块而成的复合材料；步骤为：首先采用水热反应合成出钴基氢氧化物，经过煅烧后得到纳米立方块结构的四氧化三钴材料，再通过硫代乙酰胺作为硫源，与先前制备的四氧化三钴进行水热反应即可制备出该析氧电催化剂。本发明的电催化剂由于特别的纳米立方块结构和化学组成，提供了更多的活性位点，增大了电化学活性面积，具有更高的析氧活性和稳定性；并且制备方法简便，步骤简单，操作易行，样品形貌易于调控，原材料丰富、价格低廉，有利于大规模地合成及推广使用，为新能源的开发及工业化应用奠定了良好基础。
The invention belongs to the field of electrocatalytic materials, and specifically relates to a preparation method of a sulfur-doped cobalt-based nanometer oxygen evolution electrocatalyst. The electrocatalyst is a composite material made of cobalt-based sulfide doped with cobalt tetroxide nanocubes; the steps are: first, a hydrothermal reaction is used to synthesize cobalt-based hydroxide, and after calcination, a nanocube-structured cobalt tetroxide material is obtained. The oxygen evolution electrocatalyst can be prepared by using thioacetamide as a sulfur source and performing a hydrothermal reaction with the previously prepared cobalt tetroxide. Due to the special nanocube structure and chemical composition, the electrocatalyst of the present invention provides more active sites, increases the electrochemical active area, and has higher oxygen evolution activity and stability; and the preparation method is simple and the steps are It is simple, easy to operate, the sample morphology is easy to control, the raw materials are abundant, and the price is low, which is conducive to large-scale synthesis and popularization, laying a good foundation for the development and industrial application of new energy.
Description
技术领域Technical field
本发明属于电催化材料领域，具体涉及一种硫掺杂的钴基纳米析氧电催化剂的制备方法。The invention belongs to the field of electrocatalytic materials, and specifically relates to a preparation method of a sulfur-doped cobalt-based nanometer oxygen evolution electrocatalyst.
背景技术Background technique
能源是人类生存和发展的重要物质基础，也是当今国际、经济、军事、外交关注的一个热点。当前能源危机和环境污染已日益严峻，开发可再生洁净能源已成为各国学者关注的焦点。氢能以其清洁，高效的特点被公认是未来最具潜力的理想能源载体。电解水制氢因其工艺原理简单而倍受研究者青睐。电解电压是评判电解水能耗的一个重要标准，因为有高过电位和较大的欧姆电压降存在，往往实际电解水所需电压比理论上要高出许多。提高电解水***中的能量转换效率和电解水***性能的关键是要降低反应电阻或过电位。因此，需要寻找具有低过电位的阳极催化剂来加快析氧电极反应速率以提高能量转换效率。目前，电解水产氢和氧还原反应最好的催化剂仍然是Pt系贵金属，而RuO2、IrO2等被认为是性能最好的OER电催化剂。但这些贵金属在地壳中的储量有限，价格昂贵且稳定性不好，不利于大规模生产用于电催化反应中。因此,可控制备廉价、高效、耐用、绿色环保的催化剂成为目前的研究热点之一。Energy is an important material basis for human survival and development, and it is also a hot topic of international, economic, military and diplomatic attention today. The current energy crisis and environmental pollution have become increasingly severe, and the development of renewable and clean energy has become the focus of scholars from various countries. Hydrogen energy is recognized as the ideal energy carrier with the greatest potential in the future due to its clean and efficient characteristics. Hydrogen production by electrolysis of water is favored by researchers because of its simple process principle. Electrolysis voltage is an important criterion for judging the energy consumption of electrolyzed water. Because of the existence of high overpotential and large ohmic voltage drop, the voltage required for actual electrolysis of water is often much higher than theoretically. The key to improving the energy conversion efficiency and performance of the water electrolysis system is to reduce the reaction resistance or overpotential. Therefore, there is a need to find anode catalysts with low overpotential to accelerate the oxygen evolution electrode reaction rate to improve energy conversion efficiency. At present, the best catalysts for hydrogen production and oxygen reduction reactions through electrolysis of water are still Pt-based precious metals, while RuO 2 , IrO 2 , etc. are considered to be the best-performing OER electrocatalysts. However, these precious metals have limited reserves in the earth's crust, are expensive and have poor stability, which is not conducive to large-scale production and use in electrocatalytic reactions. Therefore, the controllable preparation of cheap, efficient, durable, green and environmentally friendly catalysts has become one of the current research hotspots.
发明内容Contents of the invention
本发明的目的在于克服现有技术的不足，又能解决上述问题。故发明了一种具有一定催化活性，制备工艺简单，原料价格低廉、丰富的析氧电催化剂的制备方法。The purpose of the present invention is to overcome the shortcomings of the prior art and to solve the above problems. Therefore, a method for preparing an oxygen evolution electrocatalyst with certain catalytic activity, simple preparation process, cheap and abundant raw materials was invented.
为了实现上述目的，本发明的具体步骤如下：In order to achieve the above objects, the specific steps of the present invention are as follows:
本发明由六水合硝酸钴，氢氧化钠，硫代乙酰胺，乙醇制成，其具体步骤如下：The invention is made from cobalt nitrate hexahydrate, sodium hydroxide, thioacetamide and ethanol. The specific steps are as follows:
(1)分别将六水合硝酸钴和氢氧化钠分散在水中进行超声，得到氢氧化钠的水溶液和硝酸钴的水溶液；(1) Disperse cobalt nitrate hexahydrate and sodium hydroxide in water and conduct ultrasound respectively to obtain an aqueous solution of sodium hydroxide and an aqueous solution of cobalt nitrate;
(2)然后将氢氧化钠的水溶液匀速滴加到硝酸钴的水溶液中，并进行搅拌，得到混合溶液；(2) Then add the aqueous solution of sodium hydroxide dropwise to the aqueous solution of cobalt nitrate at a constant speed, and stir to obtain a mixed solution;
(3)将步骤(2)中的混合溶液进行水热反应，反应后经过离心，洗涤，干燥后得到前驱体粉末；(3) The mixed solution in step (2) is subjected to a hydrothermal reaction, and after the reaction, the precursor powder is obtained by centrifugation, washing, and drying;
(4)将步骤(3)中的前驱体粉末在马弗炉中煅烧，得到四氧化三钴粉末；然后分别将四氧化三钴粉末和硫代乙酰胺分散在无水乙醇中进行超声，得到四氧化三钴的乙醇溶液和硫代乙酰胺的乙醇溶液；然后将四氧化三钴的乙醇溶液和硫代乙酰胺的乙醇溶液混合，得到混合溶液；搅拌后进行水热反应；反应后得到的沉淀经过离心，洗涤和冷冻干燥，干燥后即得所需制备的硫掺杂的钴基纳米析氧电催化剂。(4) Calcining the precursor powder in step (3) in a muffle furnace to obtain tricobalt tetroxide powder; then dispersing tricobalt tetroxide powder and thioacetamide in absolute ethanol and ultrasonicating to obtain an ethanol solution of cobalt tetroxide and sulfur Substitute the ethanol solution of acetamide; then mix the ethanol solution of cobalt tetraoxide and the ethanol solution of thioacetamide to obtain a mixed solution; perform a hydrothermal reaction after stirring; the precipitate obtained after the reaction is centrifuged, washed and freeze-dried, and then dried The required sulfur-doped cobalt-based nanometer oxygen evolution electrocatalyst is obtained.
优选的，步骤(1)中，所述六水合硝酸钴与水的用量比为0.388g：1mL。Preferably, in step (1), the dosage ratio of the cobalt nitrate hexahydrate and water is 0.388g:1mL.
优选的，步骤(1)中，所述氢氧化钠与水的用量比为0.04g：1mL。Preferably, in step (1), the dosage ratio of sodium hydroxide and water is 0.04g:1mL.
优选的，步骤(2)中，所述滴加混合时，氢氧化钠的水溶液中的氢氧化钠与硝酸钴的水溶液中的硝酸钴的用量比为0.04g：0.388g；所述搅拌的时间为30～40min。Preferably, in step (2), during the dropwise mixing, the dosage ratio of sodium hydroxide in the aqueous solution of sodium hydroxide and cobalt nitrate in the aqueous solution of cobalt nitrate is 0.04g:0.388g; the stirring time It is 30~40min.
优选的，步骤(3)中，所述水热反应的温度为150～180℃，时间为5h。Preferably, in step (3), the temperature of the hydrothermal reaction is 150-180°C and the time is 5 hours.
优选的，步骤(4)中，所述四氧化三钴粉末与无水乙醇的用量比为1.5mg：1mL；Preferably, in step (4), the dosage ratio of the cobalt tetroxide powder and absolute ethanol is 1.5 mg: 1 mL;
优选的，步骤(4)中，所述硫代乙酰胺与水的用量比为1.2～14.4mg：1mL；Preferably, in step (4), the dosage ratio of thioacetamide to water is 1.2 to 14.4 mg: 1 mL;
优选的，步骤(4)中，所述四氧化三钴的乙醇溶液和硫代乙酰胺的乙醇溶液混合时，四氧化三钴的乙醇溶液中的四氧化三钴与硫代乙酰胺的乙醇溶液中的硫代乙酰胺用量比为1.5mg：1.2～14.4mg。Preferably, in step (4), when the ethanol solution of tricobalt tetroxide and the ethanol solution of thioacetamide are mixed, the dosage ratio of tricobalt tetroxide in the ethanol solution of tricobalt tetroxide to the thioacetamide in the ethanol solution of thioacetamide is: 1.5mg: 1.2～14.4mg.
优选的，步骤(4)中，所述水热反应的温度为120～150℃，时间为12h。Preferably, in step (4), the temperature of the hydrothermal reaction is 120-150°C and the time is 12 hours.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
(1)本发明采用了阴离子调节策略，通过硫离子的掺杂来调节活性位点的电子结构、增加催化活性位点的暴露并加快电子的传输速率，降低与催化剂表面OER中间体吸附和解吸有关的ΔG来提高OER催化剂的整体性能。由于其特别的纳米立方块结构和化学组成，相比四氧化三钴单体催化剂而言该材料暴露了更多的活性位点，增大了电化学活性面积；相比于其它的过渡金属电催化剂而言，该材料具有更高的析氧活性和稳定性，仅仅需要低至292mV的过电位即可在1M KOH中达到10mA cm-2的电流密度。并且其制备方法简便，步骤简单，操作易行，样品形貌易于调控；有利于在工业生产中的大规模制备，具有相当大的工业化应用潜力。(1) The present invention adopts an anion adjustment strategy to adjust the electronic structure of the active site through doping of sulfide ions, increase the exposure of the catalytic active site, speed up the electron transmission rate, and reduce the adsorption and desorption of OER intermediates on the catalyst surface. related ΔG to improve the overall performance of the OER catalyst. Due to its special nanocube structure and chemical composition, this material exposes more active sites than the cobalt tetraoxide monomer catalyst and increases the electrochemical active area; compared with other transition metal electrocatalysts , this material has higher oxygen evolution activity and stability, and only requires an overpotential as low as 292mV to reach a current density of 10mA cm -2 in 1M KOH. Moreover, the preparation method is simple, the steps are simple, the operation is easy, and the sample morphology is easy to control; it is conducive to large-scale preparation in industrial production, and has considerable industrial application potential.
(2)本发明已经证明了一种简单且具有成本效益的策略来制备硫掺杂的钴基纳米析氧电催化剂，可以通过控制反应条件来轻松实现对材料的微观结构及形貌的调控，从而提高催化剂性能。(2) The present invention has demonstrated a simple and cost-effective strategy to prepare sulfur-doped cobalt-based nano-oxygen evolution electrocatalysts, which can easily control the microstructure and morphology of the material by controlling the reaction conditions. Thereby improving the catalyst performance.
附图说明Description of drawings
图1为本发明实施例1制备的四氧化三钴单体的扫描电子显微镜图片。Figure 1 is a scanning electron microscope picture of tricobalt tetroxide monomer prepared in Example 1 of the present invention.
图2为本发明实施例1所制备的电催化材料的扫描电子显微镜图片。Figure 2 is a scanning electron microscope picture of the electrocatalytic material prepared in Example 1 of the present invention.
图3为本发明实施例1制备的四氧化三钴单体的X射线衍射图谱。Figure 3 is an X-ray diffraction pattern of tricobalt tetroxide monomer prepared in Example 1 of the present invention.
图4为本发明实施例1-4所制备的电催化材料的X射线衍射图谱。Figure 4 is an X-ray diffraction pattern of the electrocatalytic material prepared in Examples 1-4 of the present invention.
图5为本发明实施例1-4中所制备的硫的不同掺杂含量的电催化材料的析氧反应的线性扫描伏安图谱。Figure 5 is a linear scan voltammogram of the oxygen evolution reaction of electrocatalytic materials with different sulfur doping contents prepared in Examples 1-4 of the present invention.
具体实施方式Detailed ways
为了使本技术领域的人员更好的理解本发明方案，下面将结合本发明实施例中的附图，对发明实施例中的技术方案进行清楚、完整的描述，所描述的实施例仅仅是本发明的一部分实施例，而非限制性的。基于下所获得的所有其他实施例，都应当属于本发明保护的范围。In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. The described embodiments are only for the purpose of this invention. These are examples of the invention and are not limiting. All other embodiments obtained based on the following should belong to the scope of protection of the present invention.
实施例1：Example 1:
(1)溶剂热反应；(1) Solvothermal reaction;
分别将11.64g六水合硝酸钴和0.4g氢氧化钠溶于30mL和10mL水中，并搅拌10min，得到氢氧化钠的水溶液和硝酸钴的水溶液；然后将氢氧化钠溶液逐滴加到搅拌下的硝酸钴溶液中，再经过30min搅拌后将其转移到50mL聚四氟乙烯内衬的不锈钢反应釜中，然后将反应釜放入180℃恒温烘箱中保温5h；待其自然冷却至室温，取出使用高速旋转离心机进行离心，将沉淀用去离子水三次、乙醇二次进行洗涤，置于60℃真空干燥箱中24h。待样品干燥后进行充分研磨，将其平铺在坩埚中放置于马弗炉中以2℃/min升温至500℃煅烧3h，即可得纳米立方块结构的四氧化三钴粉末。Dissolve 11.64g cobalt nitrate hexahydrate and 0.4g sodium hydroxide in 30mL and 10mL water respectively, and stir for 10 minutes to obtain an aqueous solution of sodium hydroxide and an aqueous solution of cobalt nitrate; then add the sodium hydroxide solution dropwise to the stirred cobalt nitrate solution, stir it for 30 minutes, then transfer it to a 50mL polytetrafluoroethylene-lined stainless steel reactor, and then put the reactor into a 180°C constant-temperature oven for 5 hours; wait until it cools to room temperature naturally, then take it out for use Centrifuge in a high-speed rotating centrifuge, wash the precipitate three times with deionized water and twice with ethanol, and place it in a 60°C vacuum drying oven for 24 hours. After the sample is dried, grind it fully, place it flat in a crucible, place it in a muffle furnace, and heat it to 500°C for 3 hours at 2°C/min to obtain nanocube-structured cobalt tetroxide powder.
(2)硫化反应；(2) Vulcanization reaction;
以96mg硫代乙酰胺作为硫源，溶解于20mL无水乙醇中，得到硫代乙酰胺的乙醇溶液；再将60mg四氧化三钴粉末分散到40mL乙醇中并超声30min，然后加入硫代乙酰胺的乙醇溶液，搅拌，30min后将其转移到100mL聚四氟乙烯内衬的不锈钢反应釜中，将反应釜放入140℃恒温烘箱中保温12h；待其自然冷却至室温，取出使用高速旋转离心机进行离心，将沉淀用去离子水三次、乙醇二次进行洗涤，冷冻干燥24h后取出，即可得硫掺杂的钴基纳米析氧电催化剂。Use 96 mg of thioacetamide as the sulfur source, dissolve it in 20 mL of absolute ethanol, and obtain an ethanol solution of thioacetamide; then disperse 60 mg of tricobalt tetroxide powder into 40 mL of ethanol and sonicate for 30 min, and then add the ethanol solution of thioacetamide. , stir, and transfer it to a 100mL polytetrafluoroethylene-lined stainless steel reactor after 30 minutes. Put the reactor into a 140°C constant temperature oven and keep it for 12 hours; wait until it naturally cools to room temperature, then take it out and centrifuge it in a high-speed rotating centrifuge. , wash the precipitate three times with deionized water and twice with ethanol, freeze-dry it for 24 hours, and then take it out to obtain a sulfur-doped cobalt-based nanometer oxygen evolution electrocatalyst.
表征分析：Characterization analysis:
所得四氧化三钴单体催化剂和硫掺杂的钴基纳米析氧电催化剂的扫描电子显微镜照片如图1和图2所示。从图1所示扫描结果可以看出，四氧化三钴的立方块结构已成功制备，且立方块的大小均一，边长约为200nm。从图2所示扫描结果可以看出，硫掺杂的钴基纳米析氧电催化剂材料形貌发生变化，硫化物呈纳米花状结构，这可以大大增加电催化剂的比表面积和提供了更多的活性位点。The scanning electron microscope pictures of the obtained cobalt tetroxide monomer catalyst and the sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst are shown in Figures 1 and 2. It can be seen from the scanning results shown in Figure 1 that the cubic structure of cobalt tetraoxide has been successfully prepared, and the cubes are uniform in size with a side length of about 200 nm. From the scanning results shown in Figure 2, it can be seen that the morphology of the sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst material has changed, and the sulfide has a nano-flower-like structure, which can greatly increase the specific surface area of the electrocatalyst and provide more active site.
通过对四氧化三钴单体催化剂的X射线衍射光谱图3的分析可以看出，所制备的四氧化三钴呈立方相，与四氧化三钴的标准卡片(JCPDS No.50-0653)完全吻合，这意味着四氧化三钴可以通过一步水热法合成，未检测到任何杂质峰，表明制备的四氧化三钴纯度较高；硫掺杂的钴基纳米析氧电催化剂的X射线衍射图4显示出一些噪音，这可能是由于硫化物产物中复杂的多元组成所致。衍射峰可以用两个钴硫化物相的混合物标出，分别是CoS1.097和Co3S4。From the analysis of the X-ray diffraction spectrum Figure 3 of the tricobalt tetroxide monomer catalyst, it can be seen that the prepared tricobalt tetroxide is in a cubic phase, which is completely consistent with the standard card of tricobalt tetroxide (JCPDS No. 50-0653), which means that the tricobalt tetroxide can be passed through one step. Synthesized by hydrothermal method, no impurity peaks were detected, indicating that the purity of the prepared cobalt tetroxide is relatively high; Due to complex multi-component composition. The diffraction peaks can be identified by a mixture of two cobalt sulfide phases, CoS 1.097 and Co 3 S 4 .
性能测试：Performance Testing:
用相同方法制备出不同硫掺杂含量的硫掺杂的钴基纳米析氧电催化剂，作为对比。Sulfur-doped cobalt-based nano-oxygen evolution electrocatalysts with different sulfur doping contents were prepared using the same method for comparison.
所有的性能测试均在CHI 760E电化学工作站上进行，该工作站配有典型的三电极***，在1mol/L的氢氧化钾溶液的电解质中对该电催化剂材料进行析氧性能测试。其中，采用铂丝电极作为对电极，Ag/Agcl电极作为参比电极，称取制备出的电催化剂粉末4mg加入980ul的异丙醇和20ul的nafion溶液的混合溶液中，超声30min后采用微量进样针滴10ul至3mm的玻碳电极上晾干作为工作电极。在扫描速度为5mV/s。如图5所示，当电流密度为10mA/cm2,所制备的硫掺杂的钴基纳米析氧电催化剂的过电位降低至292mV，而四氧化三钴单体催化剂的过电位为425mV，表明其析氧性能得到了显著地提升。综上述结果所述，通过该方法成功制备出一种硫掺杂的钴基纳米析氧电催化剂，且催化剂具有优越的析氧反应催化活性。All performance tests were performed on a CHI 760E electrochemical workstation, which was equipped with a typical three-electrode system. The oxygen evolution performance of the electrocatalyst material was tested in the electrolyte of 1 mol/L potassium hydroxide solution. Among them, a platinum wire electrode is used as the counter electrode and an Ag/Agcl electrode is used as the reference electrode. 4 mg of the prepared electrocatalyst powder is weighed and added to a mixed solution of 980 ul of isopropyl alcohol and 20 ul of nafion solution. After ultrasonic for 30 minutes, microinjection is used. Needle-drop 10ul to 3mm glassy carbon electrode and let dry as working electrode. The scanning speed is 5mV/s. As shown in Figure 5, when the current density is 10mA/cm 2 , the overpotential of the prepared sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst is reduced to 292mV, while the overpotential of the tricobalt tetroxide monomer catalyst is 425mV, indicating that its precipitation Oxygen performance has been significantly improved. Based on the above results, a sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst was successfully prepared through this method, and the catalyst has superior catalytic activity for oxygen evolution reaction.
实施例2：Example 2:
硫掺杂的钴基纳米析氧电催化剂的制备方法与实施例1基本相同，不同之处在于：硫化步骤中以24mg的硫代乙酰胺作为硫源，溶解于20mL无水乙醇中，得到硫代乙酰胺的乙醇溶液，其余步骤相同；进一步对其进行了表征分析和性能测试，实施例2能够达到发明目的。The preparation method of the sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst is basically the same as in Example 1, except that in the sulfurization step, 24 mg of thioacetamide is used as the sulfur source and dissolved in 20 mL of absolute ethanol to obtain sulfur. The ethanol solution of acetamide was substituted, and the remaining steps were the same; further characterization analysis and performance testing were performed, and Example 2 was able to achieve the purpose of the invention.
实施例3：Example 3:
硫掺杂的钴基纳米析氧电催化剂的制备方法与实施例1基本相同，不同之处在于：硫化步骤中以192mg的硫代乙酰胺作为硫源，溶解于20mL无水乙醇中，其余步骤相同；进一步对其进行了表征分析和性能测试，实施例3能够达到发明目的。The preparation method of the sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst is basically the same as in Example 1, except that in the sulfurization step, 192 mg of thioacetamide is used as the sulfur source and dissolved in 20 mL of absolute ethanol, and the remaining steps The same; further characterization analysis and performance testing were carried out, and Example 3 can achieve the purpose of the invention.
实施例4：Example 4:
硫掺杂的钴基纳米析氧电催化剂的制备方法与实施例1基本相同，不同之处在于：硫化步骤中以288mg的硫代乙酰胺作为硫源，溶解于20mL无水乙醇中，其余步骤相同；进一步对其进行了表征分析和性能测试，实施例4能够达到发明目的。The preparation method of the sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst is basically the same as in Example 1, except that in the sulfurization step, 288 mg of thioacetamide is used as the sulfur source and dissolved in 20 mL of absolute ethanol, and the remaining steps The same; further characterization analysis and performance testing were carried out, and Example 4 can achieve the purpose of the invention.
测试结果：通过改变不同的硫掺杂量制备出了硫掺杂的钴基纳米析氧电催化剂，对其进行了X射线衍射，电子扫描显微镜结果表明硫化的成功，并且电子显微镜测试可以看出硫化程度呈现依次递进的关系。对其进行了线性伏安扫描测试，如图3所示，实施例2表明当电流密度为10mA/cm2,所制备的硫掺杂的钴基纳米析氧电催化剂的过电位降低至332mV，实施例3表明当电流密度为10mA/cm2,所制备的硫掺杂的钴基纳米析氧电催化剂的过电位降低至307mV，实施例4表明当电流密度为10mA/cm2,所制备的硫掺杂的钴基纳米析氧电催化剂的过电位降低至305mV。由此可知，不同硫掺杂量的硫掺杂的钴基纳米析氧电催化剂的析氧性能都在四氧化三钴单体催化剂的基础上得到了极大地提升，这可能是由于硫掺杂后导致的活性位点的增加以及复合材料的电子结构得到了有效的调整。这更有利于氢氧根的吸附，并提高了电子的传输速率，加快了析氧反应的动力学进程。随着硫掺杂量的不同，其呈现出不同的过电位表明硫掺杂的含量并不是越多越好，只有达到合适的掺杂量时，电催化剂的性能才会达到最佳。Test results: A sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst was prepared by changing different sulfur doping amounts, and X-ray diffraction was performed on it. The results of the scanning electron microscope showed the success of the sulfurization, and the electron microscope test can be seen. The degree of vulcanization shows a progressive relationship. A linear voltammetry scan test was performed on it, as shown in Figure 3. Example 2 shows that when the current density is 10mA/cm 2 , the overpotential of the prepared sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst is reduced to 332mV. Example 3 shows that when the current density is 10mA/cm 2 , the overpotential of the prepared sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst is reduced to 307mV. Example 4 shows that when the current density is 10mA/cm 2 , the prepared The overpotential of the sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst was reduced to 305mV. It can be seen that the oxygen evolution performance of sulfur-doped cobalt-based nano-oxygen evolution electrocatalysts with different sulfur doping amounts has been greatly improved based on the cobalt tetroxide monomer catalyst. This may be due to the sulfur doping. The increase in active sites and the electronic structure of the composite material are effectively adjusted. This is more conducive to the adsorption of hydroxyl radicals, increases the electron transfer rate, and accelerates the kinetic process of the oxygen evolution reaction. With different sulfur doping amounts, they show different overpotentials, indicating that more sulfur doping content is not better. Only when the appropriate doping amount is reached, the performance of the electrocatalyst will be optimal.
根据以上结果，可以看出本发明提出的方法避免了复杂的制备工艺，在较低的温度下(140℃)和简便易行的制备方法下成功制备出具有较高电催化析氧性能的硫掺杂的钴基纳米析氧电催化剂，有效改善了过渡金属基电催化材料制备繁琐，析氧性能差的缺陷，也为阴离子调节电子结构来改善催化性能的手段提供了新的思路。该方法制备出的硫掺杂的钴基纳米析氧电催化剂还可以应用于金属空气电池，新型电容器和新型能源等领域。Based on the above results, it can be seen that the method proposed by the present invention avoids complicated preparation processes and successfully prepares sulfur with high electrocatalytic oxygen evolution performance at a lower temperature (140°C) and a simple and easy preparation method. The doped cobalt-based nano-oxygen evolution electrocatalyst effectively improves the defects of cumbersome preparation of transition metal-based electrocatalytic materials and poor oxygen evolution performance. It also provides new ideas for anions to adjust the electronic structure to improve catalytic performance. The sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst prepared by this method can also be applied to metal-air batteries, new capacitors, new energy sources and other fields.
本发明未尽事宜为公知技术。除非特别说明，本发明采用的试剂和设备为本技术领域常规试剂和设备；所用试剂和材料均为市购。Matters not covered in the present invention are known technologies. Unless otherwise specified, the reagents and equipment used in the present invention are conventional reagents and equipment in this technical field; all reagents and materials used are commercially available.
说明：以上实施例仅用以说明本发明而并非限制本发明所描述的技术方案；因此，尽管本说明书参照上述的各个实施例对本发明已进行了详细的说明，但是本领域的普通技术人员应当理解，仍然可以对本发明进行修改或等同替换；而一切不脱离本发明的精神和范围的技术方案及其改进，其均应涵盖在本发明的权利要求范围内。Note: The above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; therefore, although the present invention has been described in detail with reference to the above-mentioned embodiments, those of ordinary skill in the art should It is understood that the present invention can still be modified or equivalently substituted; and all technical solutions and improvements that do not depart from the spirit and scope of the present invention should be covered by the claims of the present invention.
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|---|
| Facile Shape Control of Co3O4 and the Effect of the Crystal Plane on Electrochemical Performance;Xiaoling Xiao et al.;《Adv. Mater.》;20120822;第24卷;Supporting Information Synthesis of Co3O4 * |
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