CN115650316A - Method for modifying spinel oxide nickel cobaltate by using CZIF-67 - Google Patents
Method for modifying spinel oxide nickel cobaltate by using CZIF-67 Download PDFInfo
- Publication number
- CN115650316A CN115650316A CN202211237301.7A CN202211237301A CN115650316A CN 115650316 A CN115650316 A CN 115650316A CN 202211237301 A CN202211237301 A CN 202211237301A CN 115650316 A CN115650316 A CN 115650316A
- Authority
- CN
- China
- Prior art keywords
- czif
- nico
- zif
- prepared
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Inert Electrodes (AREA)
Abstract
Spinel NiCo by using CZIF-67 2 O 4 A method for carrying out the modification. 5mmol of cobalt nitrate hexahydrate and 20mmol of 2-methylimidazole (2-MIM) were weighed out and dissolved in 100mL of methanol, respectively, and stirred for 15min with a magnetic stirrer. The 2-MIM solution was then poured rapidly into Co (NO) with vigorous stirring 3 ) 2 ·6H 2 And in the O solution, stirring the mixed solution for 30min to uniformly disperse the mixed solution. Standing and aging for 24h at room temperature, centrifugally washing for a plurality of times by using methanol to obtain a purple solid, and finally drying the sample in a vacuum drying oven at 80 ℃ for 6h to obtain the ZIF-67. Placing the prepared ZIF-67 in a tube furnace, heating to 800 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, preserving heat for 3h,and after naturally cooling to room temperature, collecting black powder, and uniformly grinding the black powder by using a mortar to obtain the derivative Co-N doped carbon of the ZIF-67, wherein the derivative Co-N doped carbon is marked as CZIF-67. Mixing the prepared CZIF-67 with NiCo prepared by a sol-gel method according to the proportion of 5-15% 2 O 4 Uniformly mixing the mixture according to the mass ratio of 95-85 percent, wherein the sum of the mass ratio of the mixture and the mixture is 100 percent to prepare the CZIF-67 modified spinel NiCo 2 O 4 。
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a method for surface modification of spinel oxide NiCo by using CZIF-67 2 O 4 The method of (1).
Background
In recent years, both problems of insufficient energy reserves and environmental pollution are gradually expanding. After the industrial revolution, people consume three large fossil energy sources in large quantity, the exhaustion of the fossil energy sources is inevitable, and the world faces the crisis that no energy source is available. Since nearly half a century, people have paid more attention to resources and environmental problems, and countries develop and research the huge reputations of clean energy. Renewable energy sources such as wind energy, water energy, solar energy and the like are effectively developed and utilized. However, these new green energy sources have the disadvantages of dispersibility, non-sustainability, instability and easy diffusion, so in order to better develop and utilize these new energy sources, it is necessary to find a safe, efficient, low-cost and environmentally friendly energy conversion and storage device, so as to realize sustainable development of economy and environment. At present, the method mainly focuses on the fields of fuel cells, nickel-metal hydride batteries, metal-air batteries and the like. The metal-air battery becomes a research hotspot in the battery direction due to the advantages of rich anode materials, environmental protection, high specific energy, convenience, rapidness and the like, and overcomes the defects of certain aspects of fuel batteries. Noble metals have been a necessity for battery-type energy, but the cost is high, the materials are scarce, and the mass production is not suitable, so that the search for a substitute for noble metals is a hot point of research in recent years.
In recent years, the nickel/cobalt-based transition metal oxide has the characteristics of flexible and changeable structure, multiple valence states of metal elements and low price, and is considered to be a non-noble metal material with a great application prospect in the future. Among them, spinel type oxide NiCo 2 O 4 Has received extensive attention from researchers, a single NiCo 2 O 4 Limited exposed active sites, low conductivity and performancePoor kinetics are obtained, so that the electrocatalytic activity is slightly insufficient. The common solution strategy is to find a material with large specific surface area and good conductivity and NiCo 2 O 4 The bifunctional catalytic activity of the spinel oxide is improved through the synergistic catalytic action.
Disclosure of Invention
The invention aims to provide a method for improving spinel oxide NiCo by using CZIF-67 2 O 4 A method for catalytic performance.
The idea of the invention is as follows: by the conventional spinel oxide NiCo 2 O 4 The electrochemical performance of the oxygen electrode is improved by adding a CZIF-67 modifier.
The method comprises the following specific steps:
(1) 5mmol of cobalt nitrate hexahydrate and 20mmol of 2-methylimidazole (2-MIM) were weighed out and dissolved in 100mL of methanol, respectively, and stirred for 15min with a magnetic stirrer. The 2-MIM solution was then poured rapidly into Co (NO) with vigorous stirring 3 ) 2 ·6H 2 And gradually forming a purple solution in the O solution, and continuously stirring the mixed solution for 30min to uniformly disperse the mixed solution. And standing and aging the mixed solution at room temperature for 24h, centrifugally washing the mixed solution for a plurality of times by using methanol to obtain a purple solid, and finally drying the sample in a vacuum drying oven at the temperature of 80 ℃ for 6h to obtain the ZIF-67.
And (3) placing the prepared ZIF-67 in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, preserving heat for 3 hours, naturally cooling to room temperature, collecting black powder, and grinding the black powder uniformly by using a mortar to obtain the derivative Co-N doped carbon of the ZIF-67, wherein the mark is CZIF-67.
(2) Weighing Ni (NO) according to the molar ratio of 1 3 ) 2 ·6H 2 O and Co (NO) 3 ) 3 ·6H 2 And O, dissolving the mixture by using 40mL of deionized water and 20mL of absolute ethyl alcohol, adding 2 times of hexamethylenetetramine in the amount of the total metal ion substances into the mixture, and stirring for 15min. The solution was then transferred to a 100mL stainless steel reaction kettle lined with polytetrafluoroethylene, heated to 90 ℃ in an oven and held for 10 hours, respectively, and the reaction kettle was allowed to cool naturally to room temperature. Subsequently, the green precipitate is respectively cleaned by deionized water and absolute ethyl alcoholThe material was collected 1 to 3 times by centrifugation and the washed product was dried in a vacuum oven at 60 ℃ for 12h. Finally, placing the dried sample in a muffle furnace, heating to 350 ℃ and calcining for 2h, wherein the heating rate is 2 ℃ min -1 Naturally cooling the sample in the furnace to room temperature to obtain the flaky spinel oxide NiCo 2 O 4 。
(3) 5 to 15 percent of CZIF-67 prepared in the step (1) and spinel NiCo prepared in the step (2) 2 O 4 Uniformly mixing the materials according to the mass ratio of 95-85 percent, wherein the sum of the mass ratio of the materials is 100 percent, and preparing the CZIF-67 modified spinel.
Detailed Description
Example 1:
(1) 5mmol of cobalt nitrate hexahydrate and 20mmol of 2-methylimidazole (2-MIM) were dissolved in 100mL of methanol, respectively, and the mixture was stirred for 15min with a magnetic stirrer. Then quickly pouring the 2-MIM solution into the Co (NO 3) 2.6H 2O solution under vigorous stirring to gradually form a purple solution, and continuously stirring the mixed solution for 30min to uniformly disperse the mixed solution. Standing and aging the mixed solution at room temperature for 24h, centrifugally washing the mixed solution with methanol for a plurality of times to obtain a purple solid, and finally placing the sample in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the ZIF-67.
And (3) placing the prepared ZIF-67 in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, preserving heat for 3h, naturally cooling to room temperature, collecting black powder, grinding uniformly by using a mortar to obtain the derivative Co-N doped carbon of the ZIF-67, and marking as CZIF-67.
(2) Weighing Ni (NO) according to the molar ratio of 1 3 ) 2 ·6H 2 O and Co (NO) 3 ) 3 ·6H 2 And O, dissolving the mixture by using 40mL of deionized water and 20mL of absolute ethyl alcohol, adding 2 times of hexamethylenetetramine in the amount of the total metal ion substances into the mixture, and stirring for 15min. The solution was then transferred to a 100mL stainless steel reaction kettle lined with polytetrafluoroethylene, heated to 90 ℃ in an oven and held for 10 hours, respectively, and the reaction kettle was allowed to cool naturally to room temperature. Subsequently washing the green precipitate with deionized water and absolute ethanol for 1 to 3 times, respectively, collecting the washed product by centrifugation, and vacuum-washing at 60 deg.CAnd drying in a drying box for 12 hours. Finally, placing the dried sample in a muffle furnace, heating to 350 ℃, calcining for 2h, wherein the heating rate is 2 ℃ min -1 Naturally cooling the sample in the furnace to room temperature to obtain the flaky spinel oxide NiCo 2 O 4 。
(3) Mixing the CZIF-67 prepared in the step (1) and the spinel NiCo prepared in the step (2) 2 O 4 According to the proportion of 5%: uniformly mixing 95% of the mixture in a mass ratio of 100% to obtain the CZIF-67 modified NiCo 2 O 4 。
Example 2:
(1) 5mmol of cobalt nitrate hexahydrate and 20mmol of 2-methylimidazole (2-MIM) were weighed out and dissolved in 100mL of methanol, respectively, and stirred for 15min with a magnetic stirrer. The 2-MIM solution was then poured rapidly into Co (NO) with vigorous stirring 3 ) 2 ·6H 2 And gradually forming a purple solution in the O solution, and continuously stirring the mixed solution for 30min to uniformly disperse the mixed solution. Standing and aging the mixed solution at room temperature for 24h, centrifugally washing the mixed solution with methanol for a plurality of times to obtain a purple solid, and finally placing the sample in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the ZIF-67.
And (3) placing the prepared ZIF-67 in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, preserving heat for 3 hours, naturally cooling to room temperature, collecting black powder, and grinding the black powder uniformly by using a mortar to obtain the derivative Co-N doped carbon of the ZIF-67, wherein the mark is CZIF-67.
(2) Weighing Ni (NO) according to the molar ratio of 1 3 ) 2 ·6H 2 O and Co (NO) 3 ) 3 ·6H 2 And O, dissolving the mixture by using 40mL of deionized water and 20mL of absolute ethyl alcohol, and simultaneously adding hexamethylenetetramine with the amount of 2 times of the total substance of the metal ions into the mixture and stirring for 15min. The solution was then transferred to a 100mL teflon-lined stainless steel reaction kettle, heated to 90 ℃ in an oven and held for 10 hours, respectively, and the reaction kettle was allowed to cool naturally to room temperature. The green precipitate was then washed with deionized water and absolute ethanol 1 to 3 times, respectively, and the washed product was collected by centrifugation and dried in a vacuum oven at 60 ℃ for 12 hours. Finally, the dried sample is placed in a muffle furnace, and the temperature is raised toCalcining at 350 ℃ for 2h, wherein the heating rate is 2 ℃ min -1 Naturally cooling the sample in the furnace to room temperature to obtain the flaky spinel oxide NiCo 2 O 4 。
(3) Mixing the CZIF-67 prepared in the step (1) and the spinel NiCo prepared in the step (2) 2 O 4 According to the proportion of 10%: uniformly mixing 90% of the mixture in a mass ratio, wherein the sum of the two ratios is 100%, and preparing the CZIF-67 modified NiCo 2 O 4 。
Example 3:
(1) 5mmol of cobalt nitrate hexahydrate and 20mmol of 2-methylimidazole (2-MIM) were dissolved in 100mL of methanol, respectively, and the mixture was stirred for 15min with a magnetic stirrer. The 2-MIM solution was then poured rapidly into Co (NO) with vigorous stirring 3 ) 2 ·6H 2 And gradually forming a purple solution in the O solution, and continuously stirring the mixed solution for 30min to uniformly disperse the mixed solution. And standing and aging the mixed solution at room temperature for 24h, centrifugally washing the mixed solution for a plurality of times by using methanol to obtain a purple solid, and finally drying the sample in a vacuum drying oven at the temperature of 80 ℃ for 6h to obtain the ZIF-67.
And (3) placing the prepared ZIF-67 in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, preserving heat for 3h, naturally cooling to room temperature, collecting black powder, grinding uniformly by using a mortar to obtain the derivative Co-N doped carbon of the ZIF-67, and marking as CZIF-67.
(2) Weighing Ni (NO) according to the molar ratio of 1 3 ) 2 ·6H 2 O and Co (NO) 3 ) 3 ·6H 2 And O, dissolving the mixture by using 40mL of deionized water and 20mL of absolute ethyl alcohol, adding 2 times of hexamethylenetetramine in the amount of the total metal ion substances into the mixture, and stirring for 15min. The solution was then transferred to a 100mL teflon-lined stainless steel reaction kettle, heated to 90 ℃ in an oven and held for 10 hours, respectively, and the reaction kettle was allowed to cool naturally to room temperature. The green precipitate was then washed with deionized water and absolute ethanol 1 to 3 times, respectively, and the washed product was collected by centrifugation and dried in a vacuum oven at 60 ℃ for 12 hours. Finally, placing the dried sample in a muffle furnace, heating to 350 ℃ and calcining for 2h, wherein the heating rate is 2 ℃ min -1 When the sample in the furnace is naturally cooledCooling to room temperature to obtain the flaky spinel oxide NiCo 2 O 4 。
(3) Mixing the CZIF-67 prepared in the step (1) and the spinel NiCo prepared in the step (2) 2 O 4 According to the weight percentage of 15%:85 percent of the mixture is evenly mixed, and the sum of the proportion of the two is 100 percent to prepare the CZIF-67 modified NiCo 2 O 4 。
The catalysts prepared in the above examples were tested and the results were as follows:
(1) In the anodic polarization, the oxygen electrode added with 10% of the CZIF-67 catalyst had the highest current density reaching 275.6 mA-cm at a voltage of 1V, as compared with the other electrodes -2 。
(2) In the cathodic polarization, the oxygen electrode catalyzed by the catalyst containing 10% of CZIF-67 was charged at a voltage of-0.6V to a current density of 235.6mA cm -2 。
(3) Analysis of the test results, in NiCo 2 O 4 In addition, the CZIF-67 is added in an appropriate amount to synergistically enhance the oxygen reduction and oxygen precipitation catalytic activities of the catalyst, and the CZIF-67 added in an amount of 10% has the highest catalytic activity.
Claims (1)
1. Spinel NiCo by using CZIF-67 2 O 4 The modification method is characterized by comprising the following specific steps:
(1) Placing ZIF-67 in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, preserving heat for 3 hours, naturally cooling to room temperature, and collecting black powder, namely Co-N doped carbon serving as a derivative of ZIF-67, and marking as CZIF-67;
(2) 5-15% of CZIF-67 prepared in the step (1) and spinel oxide NiCo prepared by a sol-gel method 2 O 4 Uniformly mixing the raw materials according to the mass ratio of 95-85 percent, wherein the sum of the mass ratio of the raw materials and the raw materials is 100 percent to prepare the CZIF-67 modified NiCo 2 O 4 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211237301.7A CN115650316A (en) | 2022-10-09 | 2022-10-09 | Method for modifying spinel oxide nickel cobaltate by using CZIF-67 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211237301.7A CN115650316A (en) | 2022-10-09 | 2022-10-09 | Method for modifying spinel oxide nickel cobaltate by using CZIF-67 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115650316A true CN115650316A (en) | 2023-01-31 |
Family
ID=84986747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211237301.7A Pending CN115650316A (en) | 2022-10-09 | 2022-10-09 | Method for modifying spinel oxide nickel cobaltate by using CZIF-67 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115650316A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003455A (en) * | 2014-06-18 | 2014-08-27 | 中国环境科学研究院 | Method for preparing multi-shape controllable nano nikel-cobalt spinel oxide |
| CN107895777A (en) * | 2017-11-07 | 2018-04-10 | 北京工业大学 | One kind is based on Co in situ (II) dopen Nano porous carbon materials CZIF‑67Lead carbon battery negative pole preparation method |
| CN112691691A (en) * | 2021-01-17 | 2021-04-23 | 北京工业大学 | Preparation method of modified ZIFs-derived Co-N-C-MT/EA catalyst |
| CN114836779A (en) * | 2022-05-13 | 2022-08-02 | 安徽师范大学 | Layered double hydroxide/nitrogen-doped carbon composite material and preparation method and application thereof |
-
2022
- 2022-10-09 CN CN202211237301.7A patent/CN115650316A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003455A (en) * | 2014-06-18 | 2014-08-27 | 中国环境科学研究院 | Method for preparing multi-shape controllable nano nikel-cobalt spinel oxide |
| CN107895777A (en) * | 2017-11-07 | 2018-04-10 | 北京工业大学 | One kind is based on Co in situ (II) dopen Nano porous carbon materials CZIF‑67Lead carbon battery negative pole preparation method |
| CN112691691A (en) * | 2021-01-17 | 2021-04-23 | 北京工业大学 | Preparation method of modified ZIFs-derived Co-N-C-MT/EA catalyst |
| CN114836779A (en) * | 2022-05-13 | 2022-08-02 | 安徽师范大学 | Layered double hydroxide/nitrogen-doped carbon composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108754531B (en) | Preparation method of Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material | |
| CN111785977B (en) | Preparation method of iron-cobalt alloy/nitrogen co-doped carbon aerogel electrocatalytic material | |
| CN107739023A (en) | A kind of polyhedron bimetallic oxide and its production and use | |
| CN110137516B (en) | Iron-tin alloy loaded sulfur-nitrogen co-doped carbon electrocatalyst and preparation method thereof | |
| CN102916203B (en) | Cathode non-platinum catalyst of proton exchange membrane fuel cell and preparation method thereof | |
| CN109119642B (en) | Porous nitrogen-doped carbon-supported iron nitride catalyst and preparation method and application thereof | |
| CN110611105B (en) | Preparation method of ORR catalyst | |
| CN107321373A (en) | Doped carbon carrying transition metal boride multifunctional nano catalyst and preparation method | |
| CN113571713A (en) | PtZn-loaded nitrogen-doped carbon catalyst, preparation method thereof and hydrogen-oxygen fuel cell | |
| CN110655120B (en) | Preparation method of mesoporous spherical nickel cobaltate nano material | |
| CN114477163B (en) | Iron/nitrogen co-doped single-atom carbon catalyst and preparation method thereof | |
| CN114438516B (en) | Preparation method of porous nickel-iron-based bimetallic organic framework electrocatalyst and application of porous nickel-iron-based bimetallic organic framework electrocatalyst in water oxidation reaction | |
| CN113976122B (en) | NiO/Ni dual-function electrolytic water catalyst and preparation method thereof | |
| CN113839058B (en) | Carbon-based oxygen reduction reaction catalyst and preparation method thereof | |
| CN114068963A (en) | Preparation method and application of transition metal and compound thereof anchored nitrogen-doped carbon catalyst | |
| CN112279308A (en) | Method for preparing high-energy-storage nickel-cobalt hydroxide electrode material in large batch | |
| CN112467077A (en) | Universal electrochemical modification preparation method for effectively enhancing electricity storage performance of multiple transition metal oxides | |
| CN111952606A (en) | Fe/HKUST-1 catalyst, and preparation method and application thereof | |
| CN114420950B (en) | ZIF-8 derived Zn 3 (VO 4 ) 2 Electrocatalytic material and preparation method and application thereof | |
| CN110342589A (en) | A kind of cobalt acid nickel nano flower-like composite material and preparation method | |
| CN111250167A (en) | Fe-based bimetallic organic framework electrocatalyst and preparation and application thereof | |
| CN115650316A (en) | Method for modifying spinel oxide nickel cobaltate by using CZIF-67 | |
| CN109012683B (en) | Preparation method of cobalt molybdate hollow microsphere electrocatalyst | |
| CN113522298A (en) | Perovskite oxide/Ti3C2MXene/foamed nickel composite material and preparation method and application thereof | |
| CN113078328A (en) | Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |