CN108796551B - Sea urchin-shaped cobalt sulfide catalyst loaded on foamed nickel, preparation method thereof and application of catalyst as electrolyzed water oxygen evolution catalyst - Google Patents
Sea urchin-shaped cobalt sulfide catalyst loaded on foamed nickel, preparation method thereof and application of catalyst as electrolyzed water oxygen evolution catalyst Download PDFInfo
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- CN108796551B CN108796551B CN201810564204.6A CN201810564204A CN108796551B CN 108796551 B CN108796551 B CN 108796551B CN 201810564204 A CN201810564204 A CN 201810564204A CN 108796551 B CN108796551 B CN 108796551B
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Abstract
The invention relates to sea urchin-shaped cobalt sulfide loaded on foamed nickel, a preparation method thereof and application of the sea urchin-shaped cobalt sulfide as an electrolytic water oxygen evolution catalyst. The preparation method comprises the following steps: (1) placing the foamed nickel in an organic cleaning agent for ultrasonic cleaning to remove oil stains on the surface of the foamed nickel, and then placing the foamed nickel in a dilute acid solution for ultrasonic cleaning of impurities on the surface of the foamed nickel; (2) dissolving cobalt nitrate and thioacetamide in a mixed solvent, and stirring until the cobalt nitrate and the thioacetamide are dissolved to obtain a catalyst precursor solution; (3) transferring the catalyst precursor solution into a reaction kettle containing the processed foam nickel, and carrying out hydrothermal reaction to obtain the sea urchin-shaped cobalt sulfide loaded on the foam nickel. The sea urchin-shaped cobalt sulfide catalyst has excellent catalytic oxygen evolution performance, can be applied to catalytic electrolysis of water electrode materials, and has the advantages of low preparation cost, simple operation process and good catalytic stability.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to sea urchin-shaped cobalt sulfide loaded on foamed nickel, a preparation method of the sea urchin-shaped cobalt sulfide and application of the sea urchin-shaped cobalt sulfide as an electrolytic water oxygen evolution catalyst.
Background
Fossil energy sources such as coal, oil, natural gas and the like support the progress of modern human civilization and the development of economic society. However, fossil energy faces the crisis of exhaustion and is also accompanied by serious environmental problems due to its non-regenerability and the enormous consumption of fossil energy by humans. The energy structure mainly based on fossil energy has obvious unsustainability. Limited fossil energy storage forces humans to seek new energy sources that are renewable and environmentally friendly. At present, conversion, storage and utilization of large-scale intermittent energy are all required to be solved by an efficient cleaning method, while hydrogen production by water electrolysis provides a feasible and effective solution for the above problems, but in the hydrogen production by water electrolysis, too high anode oxygen evolution overpotential needs to consume higher electric energy, so that the energy conversion efficiency is low. The noble metal anode has good activity and stability as an electrolytic water oxygen evolution catalytic electrode material, but is expensive and scarce, so that the noble metal anode is not beneficial to mass production. The non-noble metal cobalt compound of the traditional alkaline electrolyzed water anode catalyst has excellent catalytic activity and low price, and is widely researched.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art and provides urchin-shaped cobalt sulfide loaded on foamed nickel, a preparation method thereof and application of the urchin-shaped cobalt sulfide as an electrolytic water oxygen evolution catalyst.
The technical scheme adopted by the invention for solving the problems is as follows:
a preparation method of sea urchin-shaped cobalt sulfide loaded on foamed nickel mainly comprises the following steps:
(1) pretreatment of carrier foam nickel: slicing and cleaning the foamed nickel;
(2) preparation of catalyst precursor solution: dissolving cobalt nitrate and thioacetamide in a solvent, and stirring until the cobalt nitrate and the thioacetamide are dissolved to obtain a catalyst precursor solution;
(3) preparation of sea urchin-shaped cobalt sulfide catalyst loaded on foamed nickel: transferring the catalyst precursor solution into a reaction kettle containing carrier foam nickel, and carrying out hydrothermal reaction to obtain the sea urchin-shaped cobalt sulfide catalyst loaded on the foam nickel.
According to the scheme, the pretreatment of the carrier foamed nickel in the step (1) is specifically as follows: slicing foamed nickel, ultrasonic cleaning in organic cleaning agent to remove oil stain on surface, and diluting foamed nickelAnd ultrasonically cleaning impurities on the surface of the steel plate in an acid solution. Wherein the organic cleaning agent is preferably acetone or absolute ethyl alcohol and the like, and the ultrasonic cleaning time is preferably 5-15 min; the preferable concentration of the dilute acid solution is 2-4 mol.L-1The ultrasonic cleaning time is preferably 5-15min, such as dilute hydrochloric acid.
According to the scheme, the cobalt nitrate is cobalt nitrate hexahydrate, the mass ratio of the cobalt nitrate hexahydrate to thioacetamide is 1:3 to 3:1, and the preferred mass ratio is 3: 2.
According to the scheme, the solvent in the step (2) is water, alcohol or a mixed solvent. Wherein, the mixed solvent is preferably prepared by mixing distilled water and alcohol which is mutually soluble with water according to any proportion; further preferably, the volume ratio of distilled water to water-miscible alcohol in the mixed solvent is most preferably 1: 1.
According to the scheme, the hydrothermal reaction condition in the step (3) is that the reaction temperature is 120-180 ℃, and the reaction time is 2-6 h; the reaction temperature is most preferably 150 ℃ and the reaction time is 4 h.
The sea urchin-shaped cobalt sulfide loaded on the foamed nickel, which is obtained by the preparation method, is uniformly loaded on a foamed nickel framework, the average radius of a sea urchin sphere is about 2-4 mu m, and the sea urchin-shaped sphere contains a plurality of nanowires growing outwards from the center.
The invention also aims to provide application of the sea urchin-shaped cobalt sulfide loaded on the foamed nickel as an electrolytic water oxygen evolution catalyst, which can be applied to electrode materials such as lithium batteries, electrolytic water hydrogen production catalytic electrode materials and super capacitors.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the foamed nickel is used as a substrate framework, the sea urchin-shaped cobalt sulfide is uniformly loaded on the surface of the foamed nickel through hydrothermal reaction, compared with a cobalt sulfide catalyst synthesized by other two-step hydrothermal synthesis methods, the sea urchin-shaped cobalt sulfide loaded on the foamed nickel has large synthesis specific surface area, more active surfaces are exposed, the reduction of internal resistance of the catalyst improves the conductivity of the catalyst, and the catalytic performance of a non-noble metal cobalt compound is integrally improved.
Secondly, the application of the sea urchin-shaped cobalt sulfide loaded on the foamed nickel as the electrolytic water oxygen evolution catalyst avoids catalyst polymerization in the catalytic reaction process, and has low cost, high efficiency and stability; and the sea urchin-shaped cobalt sulfide catalyst is directly loaded on the foamed nickel and is not easy to fall off, and when the catalyst is used as a catalyst, no adhesive exists, so that more active surfaces can be exposed, the internal resistance is reduced, the transfer kinetics and the catalytic performance stability are improved, and the catalytic oxygen evolution performance is excellent.
Thirdly, the preparation method of the sea urchin-shaped cobalt sulfide loaded on the foamed nickel has low cost and simple preparation process.
Drawings
FIG. 1 is an XRD pattern of sea urchin-like cobalt sulfide supported on nickel foam in example 1;
FIGS. 2(a) and 2(b) are scanning electron microscope images of sea urchin-like cobalt sulfide supported on nickel foam in example 1;
FIG. 3 shows the concentration of echinoid cobalt sulfide supported on nickel foam in 1.0mol L in examples 1, 3 and 4-1Linear sweep voltammogram under KOH electrolyte;
FIG. 4 is a time-current curve of the sea urchin-like cobalt sulfide supported on the nickel foam in example 1, and the constant voltage tested was 1.55V.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. It should be noted that technical features or combinations of technical features described in the following embodiments should not be considered as being isolated, and they may be combined with each other to achieve better technical effects.
Example 1
A preparation method of sea urchin-shaped cobalt sulfide loaded on foamed nickel comprises the following steps:
(1) slicing foamed nickel into 3cm × 3cm, ultrasonic cleaning with 40ml anhydrous ethanol to remove oil stain on the surface, and placing the foamed nickel in 3mol · L-1Ultrasonically cleaning impurities on the surface by using a hydrochloric acid solution;
(2) respectively dissolving 0.3g of cobalt nitrate hexahydrate and 0.2g of thioacetamide in a mixed solvent of 20mL of distilled water and 20mL of absolute ethyl alcohol, and stirring for 15 minutes until the cobalt nitrate hexahydrate and the thioacetamide are dissolved to obtain a pink catalyst precursor solution;
(3) transferring the catalyst precursor solution into a 100mL polytetrafluoroethylene-lined reaction kettle, simultaneously placing a piece of foamed nickel treated in the step (1) in the reaction kettle, then carrying out hydrothermal reaction for 4h at the temperature of 150 ℃, cooling to room temperature, taking out a sample, washing with water and ethanol for 6 times, and drying at the temperature of 60 ℃ to obtain the sea urchin-shaped cobalt sulfide loaded on the foamed nickel.
Appearance characterization and performance test: the crystal structure of the sea urchin-shaped cobalt sulfide supported on the foamed nickel obtained in the example is characterized by MSAL-XD2, and the results are shown in figure 1, wherein 2 theta is 29.7 degrees, 31.1 degrees, 39.5 degrees, 47.6 degrees and 54.6 degrees respectively correspond to diffraction crystal faces of (311), (222), (331), (511), (531) (JCPDS No.02-1459) of the cobalt sulfide; in addition, 2 θ ═ 44.5 °,51.8 °, 76.4 ° correspond to the (111), (200), (220) (JCPDS No.65-2865) diffraction crystal planes of the base nickel foam, respectively, demonstrating that cobalt sulfide was successfully supported on the nickel foam.
According to the invention, SEM-XL30S scanning electron microscope is adopted to represent the appearance of sea urchin-shaped cobalt sulfide loaded on foamed nickel, as shown in FIG. 2, it can be seen from FIG. 2(a) that sea urchin-shaped cobalt sulfide is uniformly loaded on a foamed nickel skeleton, and the average radius of a sea urchin sphere is about 3 μm; the sea urchin shaped sphere in fig. 2(b) contains many nanowires growing outward from the center, possibly providing many active sites for catalytic reaction.
Sea urchin-shaped cobalt sulfide samples loaded on foamed nickel obtained in examples 1, 3 and 4 and ruthenium oxide loaded on foamed nickel were used as working electrodes, carbon rods were used as auxiliary electrodes, and Hg/Hg were used as2Cl2As a reference electrode, firstly 1.0 mol.L-1KOH is used as electrolyte, and three electrode bodies are formed and are tied on a Chenghua CHI66D electrochemical workstation to carry out electrochemical performance test. The linear scanning curve is shown in fig. 3, and it can be seen that the catalytic oxygen evolution performance of example 1 is rapidly improved with the increase of voltage, wherein the sea urchin-shaped cobalt sulfide loaded on the foamed nickel in example 1 is compared with that of example 3Example 4 and noble metal ruthenium oxide the catalytic oxygen evolution performance is best at a higher current density, which reaches 200mA/cm2When the voltage is lower than the predetermined value, the corresponding voltage value is 1.74V.
The test result of the continuous catalytic oxygen evolution stability of the sample of the echinoid cobalt sulfide loaded on the foamed nickel obtained in the example 1 is shown in fig. 4, and the current density of the echinoid cobalt sulfide loaded on the foamed nickel is kept stable after the continuous catalytic oxygen evolution is carried out for 14 hours, which shows that the echinoid cobalt sulfide has good durability and can be applied to industrial catalytic electrolytic water materials.
Example 2
The present embodiment is different from embodiment 1 in that: the organic cleaning agent in the step (1) is acetone, and other conditions are the same as those in the example 1.
Example 3
The present embodiment is different from embodiment 1 in that: the solvent in the step (2) is distilled water, and other conditions are the same as those in the example 1.
Example 4
The present embodiment is different from embodiment 1 in that: the solvent in the step (2) is absolute ethyl alcohol, and other conditions are the same as those in the example 1.
Example 5
The present embodiment is different from embodiment 1 in that: the mass ratio of the cobalt nitrate hexahydrate to the thioacetamide is 1: 3; the hydrothermal reaction condition is that the reaction temperature is 140 ℃ and the reaction time is 6 h; 1.0mol L of sea urchin-shaped cobalt sulfide supported on foamed nickel-1Linear sweep voltammetry curve under KOH electrolyte, current density reaching 100mA/cm2The corresponding voltage value was 1.72V, and the other conditions were the same as in example 1.
Example 6
The present embodiment is different from embodiment 1 in that: the mass ratio of the cobalt nitrate hexahydrate to the thioacetamide is 3: 1; the hydrothermal reaction condition is that the reaction temperature is 160 ℃, and the reaction time is 3 hours; 1.0mol L of sea urchin-shaped cobalt sulfide supported on foamed nickel-1Linear sweep voltammetry curve under KOH electrolyte, current density reaching 100mA/cm2When the voltage value is 1.71V; other conditions and implementationsExample 1 is the same.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A preparation method of sea urchin-shaped cobalt sulfide loaded on foamed nickel is characterized by mainly comprising the following steps:
(1) pretreatment of carrier foam nickel: slicing and cleaning the foamed nickel;
(2) preparation of catalyst precursor solution: dissolving cobalt nitrate hexahydrate and thioacetamide in a mixed solvent, and stirring until the cobalt nitrate hexahydrate and the thioacetamide are dissolved to obtain a catalyst precursor solution; the mixed solvent is formed by mixing distilled water and absolute ethyl alcohol according to the volume ratio of 1:1, and the ratio of the cobalt nitrate hexahydrate to the mixed solvent is 0.3 g: 40mL, the ratio of 0.2g thioacetamide to the mixed solvent is 0.2 g: 40 mL;
(3) preparation of sea urchin-shaped cobalt sulfide catalyst loaded on foamed nickel: transferring the catalyst precursor solution into a reaction kettle containing carrier foam nickel, and carrying out hydrothermal reaction to obtain a sea urchin-shaped cobalt sulfide catalyst loaded on the foam nickel; wherein the hydrothermal reaction condition is that the reaction temperature is 120-180 ℃, and the reaction time is 2-6 h.
2. The method for preparing echinoid cobalt sulfide supported on nickel foam as claimed in claim 1, wherein the hydrothermal reaction condition in step (3) is reaction temperature of 150 ℃ and reaction time of 4 h.
3. The preparation method of sea urchin-shaped cobalt sulfide supported on nickel foam according to claim 1, characterized in that the pretreatment of the carrier nickel foam in step (1) is specifically: slicing the foamed nickel, placing the sliced foamed nickel in an organic cleaning agent for ultrasonic cleaning to remove oil stains on the surface of the foamed nickel, and then placing the foamed nickel in a dilute acid solution for ultrasonic cleaning to remove impurities on the surface of the foamed nickel.
4. The preparation method of sea urchin-shaped cobalt sulfide loaded on foamed nickel according to claim 3, characterized in that the organic cleaning agent is acetone or absolute ethyl alcohol, and the ultrasonic cleaning time is 5-15 min; the concentration of the dilute acid solution is 2-4 mol.L-1And the ultrasonic cleaning time is 5-15 min.
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| CN109518207B (en) * | 2018-12-20 | 2019-10-25 | 华中科技大学 | A kind of efficient oxygen evolution reaction elctro-catalyst and preparation method thereof |
| CN109847778B (en) * | 2019-01-04 | 2022-07-01 | 华中师范大学 | Cobalt disulfide/carbon nitrogen composite material for oxygen evolution by electrolyzing water and synthetic method thereof |
| CN110404564B (en) * | 2019-08-16 | 2022-12-13 | 澳门大学 | Double-function full-electrolysis water-electricity catalyst and preparation method and application thereof |
| CN111408362A (en) * | 2020-03-23 | 2020-07-14 | 山东鲁北国际新材料研究院有限公司 | Sea urchin-shaped cobalt sulfide-charcoal composite material and preparation method and application thereof |
| CN111686773B (en) * | 2020-07-14 | 2021-11-16 | 南京林业大学 | Sea urchin-like nickel-iron phosphonate photocatalyst and preparation method thereof |
| CN112962115B (en) * | 2021-02-09 | 2022-04-01 | 上海交通大学 | Foamed nickel loaded sulfide electrocatalyst and preparation method and application thereof |
| CN114360919A (en) * | 2021-11-22 | 2022-04-15 | 沈阳工程学院 | Preparation method of high-performance electrode material with nano sea urchin structure |
| CN114990622A (en) * | 2022-06-02 | 2022-09-02 | 蚌埠学院 | Preparation method of sea urchin-shaped iron-doped nickel hydroxide oxygen evolution catalyst |
| CN115786964B (en) * | 2023-02-06 | 2023-12-12 | 北京化工大学 | Cobalt-based spinel Cu 0.7 Co 2.3 O 4 Electrocatalyst, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289658A (en) * | 2015-10-23 | 2016-02-03 | 吉林大学 | Carbon fiber supported cobalt sulfide nanosheet catalyst and application thereof |
| CN107201573A (en) * | 2017-05-08 | 2017-09-26 | 同济大学 | A kind of preparation method and applications of cobalt disulfide and carbon nano-fiber composite material |
| CN107337190A (en) * | 2017-07-10 | 2017-11-10 | 佛山市利元合创科技有限公司 | A kind of preparation method of the cobalt phosphate nickel grown in nickel foam of nano flower-like |
-
2018
- 2018-06-04 CN CN201810564204.6A patent/CN108796551B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289658A (en) * | 2015-10-23 | 2016-02-03 | 吉林大学 | Carbon fiber supported cobalt sulfide nanosheet catalyst and application thereof |
| CN107201573A (en) * | 2017-05-08 | 2017-09-26 | 同济大学 | A kind of preparation method and applications of cobalt disulfide and carbon nano-fiber composite material |
| CN107337190A (en) * | 2017-07-10 | 2017-11-10 | 佛山市利元合创科技有限公司 | A kind of preparation method of the cobalt phosphate nickel grown in nickel foam of nano flower-like |
Non-Patent Citations (2)
| Title |
|---|
| Facile controlled synthesis of a hierarchical porous nanocoral-like Co3S4 electrode for high-performance supercapacitors;Guijing Liu等;《RSC Adv.》;20160520;第6卷(第59期);实验部分四硫化三钴的制备和结论部分 * |
| Hydrothermal synthesis and characterization of nickel and cobalt sulfides nanocrystallines;Xiaohe Liu;《Materials Science and Engineering B》;20050515;第119卷(第1期);第2.2节Co9S8的制备、第22页左栏及图6、第23页右栏第1段 * |
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