CN110690463A - Preparation method of carbon hollow sphere composite material with low platinum loading capacity, product and application - Google Patents
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Abstract
A preparation method of a carbon hollow sphere composite material with low platinum loading capacity comprises the following steps of firstly preparing a silicon dioxide sphere which is modified by graphene, doped by nickel and cobalt and covered by carbon-nitrogen compound; then, ultrasonically dispersing the platinum precursor and a platinum compound in ethanol to form a nano platinum precursor; carrying out thermal reaction on the precursor in formamide, and dispersing platinum-nickel-cobalt alloy formed by the reaction of platinum ions and nickel and cobalt in a system; and finally, mixing the mixture with soluble starch and dicyandiamide, and forming platinum-nickel-cobalt alloy nanoparticles highly dispersed in a carbon-nitrogen compound under high-temperature pyrolysis, wherein the soluble starch and dicyandiamide form a compound similar to a graphene nanosheet after high-temperature pyrolysis and cover the surface of the catalyst, so that the stability of the catalyst is correspondingly improved. The catalyst has the advantages of low platinum content, obviously improved activity stability, excellent ORR electrical activity and stability, low cost and simple process, and is an ORR electro-catalyst with important application value.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy materials, and particularly relates to a preparation method and application of a carbon hollow sphere composite material with low platinum loading.
Background
Oxygen Reduction Reaction (ORR) is a chemical process with important applications, which is an essential reaction in many new electrochemical energy systems. For example, fuel cells, including various alcohol (methanol, ethanol, etc.) fuel cells and hydrogen-oxygen fuel cells, as well as metal-air cells, etc., have a cathode reaction that is ORR. The performance of these cells is critically affected by whether ORR can be performed efficiently and rapidly. Generally, ORR itself is a slow kinetic process, and whether or not ORR can be rapidly performed in a battery system depends mainly on the performance of an electrocatalyst, so that it is of practical importance to research and develop a novel material having excellent electrocatalytic activity for ORR.
Among the metal materials, platinum has the most effective electrocatalytic activity for ORR, and is mainly reflected in that the overpotential of platinum for ORR is small and the current density is large. However, the practical application of platinum as an electrocatalytic material for ORR is greatly limited, mainly because the resource of platinum on earth is small, and the resource distribution of platinum is greatly unbalanced, resulting in high cost of platinum, so that it is not practical to apply platinum on a large scale. Therefore, it is of great practical interest to develop ORR catalysts that are non-platinum, or have a small platinum content.
The non-platinum catalyst refers to an ORR catalyst containing no metal platinum, and due to its low cost and wide resource of the components of the catalyst, intensive research and development have been conducted on them, and a large number of catalytic materials in this area have been reported. However, these non-platinum catalysts have not been ideal when applied to the actual ORR system, and far from the performance of platinum materials. This is mainly because such materials, without the presence of platinum, lead to poor stability of catalytic ORR, because in practical battery systems, a large amount of oxygen is reduced by the catalyst, and while oxygen is reduced to water, a certain amount of intermediate hydrogen peroxide is also produced, which produces a severe poisoning effect on such non-platinum catalysts, thereby significantly reducing the activity of the catalyst. Therefore, such non-platinum catalysts have not been practically used in battery systems.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon hollow sphere composite material with low platinum loading, and also aims to provide a preparation method and application of the carbon hollow sphere composite material with low platinum loading.
To achieve the above object, the embodiments of the present invention are: a preparation method of a carbon hollow sphere composite material with low platinum loading comprises the following steps:
(1) nickel cobalt doped polydopamine coated silica spheres (PDA-Co) were prepared according to a modified prior art (Wei Wu, Wei Zhang, Yu Long, et al, Journal of colloid and Interface Science 531 (2018) 642-653)3Ni1@SiO2）；
(2) The above PDA-Co3Ni1@SiO2500mg of solid was added to a concentration of 0.5 mg X mL-1The graphene oxide dispersion liquid is fully stirred and centrifuged, and the obtained solid is 40 percentoVacuum drying under C, then under nitrogen atmosphere, at 5oC×min-1The temperature is increased to 850 ℃, then the constant temperature is kept for a certain time, the mixture is naturally cooled to the room temperature, and the obtained solid is recorded as rGO/Co3Ni1/C-N@SiO2；
(3) Mixing the above rGO/Co3Ni1/C-N@SiO2Mixing the solid with absolute ethyl alcohol, performing ultrasonic treatment to uniformly disperse the solid, then adding a platinum compound, performing ultrasonic treatment on the obtained mixture, evaporating the ethyl alcohol, and performing vacuum drying at room temperature to obtain the solid as a nano platinum precursor; rGO/Co in mixed solution3Ni1/C-N@SiO2The mass ratio to the platinum compound is 50: 1 ~ 5;
(4) ultrasonically dispersing the nano platinum precursor in formamide, heating to 135 ℃, performing a reflux reaction, centrifuging, and recording the obtained solid as Pt/rGO/Co3Ni1/C-N@SiO2；
(5) Ultrasonically dispersing soluble starch and dicyandiamide in absolute ethyl alcohol, and then adding the Pt/rGO/Co3Ni1/C-N@SiO2Performing ultrasonic treatment, and finally evaporating ethanol to obtain a solid mixture which is recorded as a catalyst precursor; the soluble starch is dicyandiamide Pt/rGO/Co3Ni1/C-N@SiO2The mass ratio of (1: 10), (20 ~ 60);
(6) the catalyst precursor was reacted in a nitrogen atmosphere at a temperature of 4 deg.CoC×min-1Heating to 800 deg.C, keeping the temperature for a certain time, naturally cooling to room temperatureThe obtained black powder was immersed in 4 mol × L-1After slowly stirring thoroughly at room temperature, the resulting solution was centrifuged, washed with water to neutrality, and the resultant solution was dissolved in KOH solution (50)oAnd C, vacuum drying is carried out, and the obtained black powder is the carbon hollow sphere composite material with low platinum loading.
In the step (3), the platinum compound is chloroplatinic acid (H)2PtCl6×6H2O), or platinum chloride (PtCl)4) Or trimethylmethylcyclopentadienyl platinum (C)9H16Pt), or trimethyl platinum iodide (C)3H9IPt）C3H9IPt）。
In the step (1), firstly, preparing the silica spheres with the diameter of 360-380 nm, namely slowly dripping tetraethoxysilane into a mixed solution consisting of ethanol, water and ammonia water containing 25wt percent of ammonia while continuously stirring, continuously stirring at a constant speed, centrifugally separating the obtained solid, washing with water and ethanol for multiple times in sequence, wherein the washing speed is 50 percentoVacuum drying is carried out under C to obtain silicon dioxide balls; the volume ratio of ethyl orthosilicate, ethanol, water and ammonia water containing 25wt% of ammonia is 20: 250: 100: 13.
then, ultrasonically dispersing the silicon dioxide spheres in water to form uniform dispersion liquid; followed by the addition of NiCl2×6H2O and CoCl2×6H2Continuously performing ultrasonic treatment, adding dopamine after the dopamine is completely dissolved, and continuously performing ultrasonic treatment to completely dissolve the dopamine; adding under stirring tris (hydroxymethyl) methylamine, stirring the solution at constant speed thoroughly, centrifuging, washing the obtained solid with water, 40%oVacuum drying under C to obtain PDA-Co3Ni1@SiO2。
The carbon hollow sphere composite material with low platinum loading is prepared according to the method.
The carbon hollow sphere composite material with low platinum loading prepared by the method is applied to electrocatalysis of oxygen reduction reaction.
According to the characteristic that a hollow carbon sphere precursor material simultaneously doped with nickel/cobalt/nitrogen has excellent electrocatalytic activity on oxygen reduction reaction, a small amount of platinum is combined with the precursor material through further solvothermal reaction and high-temperature thermal reaction, so that the unique advantages of the platinum in the aspect of electrocatalytic reaction of oxygen reduction reaction and the synergistic effect between the platinum and nickel and cobalt are fully exerted, and the carbon hollow sphere composite material with ultra-low platinum loading is prepared. Metal nickel cobalt ions are embedded in situ in the polydopamine forming process, so that metal is tightly combined with nitrogen in the subsequent high-temperature pyrolysis process, and a large number of metal-nitrogen sites with electrocatalytic activity on oxygen reduction reaction are generated; then, a small amount of platinum is doped into the carbon material through a solvothermal reaction and a high-temperature pyrolysis reaction, and forms platinum-nickel or platinum-cobalt alloy nano particles which can greatly enhance the electro-catalytic activity with metal nickel and cobalt; and finally, the carbon-nitrogen compound nanosheets generated by pyrolysis of starch and dicyandiamide at high temperature are coated on the surface of the material, so that the stability of the material is improved, metal-nitrogen active sites which are favorable for oxygen reduction reaction are generated between the coating and the material under the action of high temperature, and the electrocatalytic activity of the material is further improved. The final result ensures that the formed catalyst not only has the excellent electrocatalytic activity of the non-noble metal nickel-cobalt-carbon nitrogen material, but also greatly enhances the electrocatalytic performance of the oxygen reduction reaction of the material by adding a small amount of platinum, so that the overpotential of the oxygen reduction reaction is obviously reduced. The composite material has the characteristics of low cost and simple preparation process, and has wide application prospect in the fields of material electrochemistry and electrochemical energy.
Detailed Description
Example 1
(1) Nickel cobalt doped polydopamine coated silica spheres (PDA-Co) were prepared according to a modified prior art (Wei Wu, Wei Zhang, Yu Long, et al, Journal of colloid and Interface Science 531 (2018) 642-653)3Ni1@SiO2）：
Firstly, preparing a silica ball with the diameter of 360-380 nm, namely slowly dripping 20 mL of tetraethoxysilane into a mixed solution consisting of 250 mL of ethanol, 100 mL of water and 13 mL of ammonia water (containing 25wt percent of ammonia) under continuous stirring, continuing to stir at a constant speed for 3 hours after dripping is finished, and centrifugally separating the obtained solidSequentially washing with water and ethanol for 3 times, 50 timesoVacuum drying for 24 hours under C to obtain silicon dioxide spheres;
then, 1g of the silica spheres was ultrasonically dispersed in 2000mL of water to form a uniform dispersion; followed by the addition of 0.1 g of NiCl2×6H2O and 0.3 g CoCl2×6H2Continuously performing ultrasonic treatment, after the dopamine is completely dissolved, adding 1g of dopamine, and continuously performing ultrasonic treatment to completely dissolve the dopamine; then 2.5 g of tris (hydroxymethyl) methylamine are added with stirring, the solution is stirred continuously at constant speed for 24 hours and finally centrifuged, the solid obtained is washed 3 times with water, 40 timesoVacuum drying for 24 hours under C to obtain PDA-Co3Ni1@SiO2
(2) The above PDA-Co3Ni1@SiO2500mg of solid was added to 50 mL of 0.5 mg X mL-1After stirring for 3 hours, the resulting solid was centrifuged to obtain a solid of 40oVacuum drying for 12 hours under C, then transferring to a tube furnace under nitrogen atmosphere at 5oC×min-1The temperature is increased to 850 ℃, the temperature is kept for 2 hours, the mixture is naturally cooled to the room temperature, and the obtained solid is marked as rGO/Co3Ni1/C-N@SiO2；
(3) 500mg of the above rGO/Co3Ni1/C-N@SiO2The solid was mixed with 50 mL of absolute ethanol, sonicated to uniformly disperse the solid, and then 10 mg of chloroplatinic acid (H) was added2PtCl6×6H2And O), ultrasonically treating the obtained mixture for 4 hours, evaporating ethanol, and carrying out vacuum drying at room temperature to obtain a solid which is recorded as a nano platinum precursor.
(4) Ultrasonically dispersing the nano platinum precursor in 30mL formamide, heating to 135 ℃, performing reflux reaction for 10 hours, and centrifuging to obtain a solid recorded as Pt/rGO/Co3Ni1/C-N@SiO2；
(5) Ultrasonically dispersing soluble starch and dicyandiamide in absolute ethyl alcohol, and then adding the Pt/rGO/Co3Ni1/C-N@SiO2Keeping soluble starch of dicyandiamide Pt/rGO/Co3Ni1/C-N@SiO2In a mass ratio of 1:10: 20; and (4) performing ultrasonic treatment, and finally evaporating ethanol to obtain a solid mixture which is recorded as a catalyst precursor.
(6) Transferring the catalyst precursor into a tubular furnace, and performing reaction in a nitrogen atmosphere by using a reaction condition of 4oC×min-1Heating to 800 deg.C, maintaining at the temperature for 2 hr, naturally cooling to room temperature, and soaking the obtained black powder in 4 mol × L-1After slowly stirring at room temperature for 20 hours, the resulting solution was centrifuged, washed with water to neutrality, and the resulting solution was stirred at 50 deg.CoAnd C, vacuum drying for 12 hours, wherein the obtained black powder is the carbon hollow sphere composite material with low platinum loading.
(7) The prepared carbon hollow sphere composite material with low platinum loading is used for testing the electrocatalytic activity of ORR in a three-electrode system, wherein the counter electrode is a platinum sheet, the reference electrode is an Ag/AgCl (sat. KCl) electrode, the working electrode is a rotary glassy carbon electrode coated with the carbon hollow sphere composite material with low platinum loading on the surface, and the electrocatalytic activity of the carbon hollow sphere composite material with low platinum loading on the oxygen reduction reaction is measured in different oxygen saturated electrolyte solutions.
The test results are listed in the following table:
example 2
Steps (1) and (2) are the same as steps (1) and (2) of example 1, respectively.
(3) 500mg of the above rGO/Co3Ni1/C-N@SiO2The solid was mixed with 50 mL of absolute ethanol, sonicated to uniformly disperse the solid, and then 25 mg of chloroplatinic acid (H) was added2PtCl6×6H2O), carrying out ultrasonic treatment on the obtained mixture for 4 hours, evaporating ethanol, and carrying out vacuum drying at room temperature to obtain a solid which is recorded as a nano platinum precursor.
Steps (4), (5), (6) and (7) are the same as steps (4), (5), (6) and (7) of example 1, respectively.
The test results are listed in the following table:
example 3
Steps (1) and (2) are the same as steps (1) and (2) of example 1, respectively.
(3) 500mg of the above rGO/Co3Ni1/C-N@SiO2The solid was mixed with 50 mL of absolute ethanol, sonicated to uniformly disperse the solid, and then 50 mg of chloroplatinic acid (H) was added2PtCl6×6H2And O), ultrasonically treating the obtained mixture for 4 hours, evaporating ethanol, and carrying out vacuum drying at room temperature to obtain a solid which is recorded as a nano platinum precursor.
Steps (4), (5), (6) and (7) are the same as steps (4), (5), (6) and (7) of example 1, respectively.
The test results are listed in the following table:
example 4
Steps (1), (2), (3) and (4) are the same as steps (1), (2), (3) and (4) of example 2, respectively.
(5) Ultrasonically dispersing soluble starch and dicyandiamide in absolute ethyl alcohol, and then adding the Pt/rGO/Co3Ni1/C-N@SiO2Keeping soluble starch of dicyandiamide Pt/rGO/Co3Ni1/C-N@SiO2The mass ratio of (1: 10: 40); and (4) performing ultrasonic treatment, and finally evaporating ethanol to obtain a solid mixture which is recorded as a catalyst precursor.
Steps (6) and (7) are the same as steps (6) and (7) of example 1, respectively.
The test results are listed in the following table:
example 5
Steps (1), (2), (3) and (4) are the same as steps (1), (2), (3) and (4) of example 2, respectively.
(5) Ultrasonically dispersing soluble starch and dicyandiamide in absolute ethyl alcohol, and then adding the Pt/rGO/Co3Ni1/C-N@SiO2Keeping soluble starch of dicyandiamide Pt/rGO/Co3Ni1/C-N@SiO2The mass ratio of (1: 10: 60); and (4) performing ultrasonic treatment, and finally evaporating ethanol to obtain a solid mixture which is recorded as a catalyst precursor.
Steps (6) and (7) are the same as steps (6) and (7) of example 1, respectively.
The test results are listed in the following table:
example 6
Steps (1) and (2) are the same as steps (1) and (2) of example 1, respectively.
(3) 500mg of the above rGO/Co3Ni1/C-N@SiO2The solid was mixed with 50 mL of absolute ethanol, sonicated to disperse the solid uniformly, and then 25 mg of platinum chloride (PtCl) was added4) And after the obtained mixture is subjected to ultrasonic treatment for 4 hours, evaporating ethanol, and performing vacuum drying at room temperature to obtain a solid which is recorded as a nano platinum precursor.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 4.
Steps (6) and (7) are the same as steps (6) and (7) of example 1, respectively.
The test results are listed in the following table:
example 7
Steps (1) and (2) are the same as steps (1) and (2) of example 1, respectively.
(3) 500mg of the above rGO/Co3Ni1/C-N@SiO2The solid was mixed with 50 mL of absolute ethanol, sonicated to uniformly disperse the solid, and then 25 mg of trimethylmethylcyclopentadienyl platinum (C) was added9H16Pt), ultrasonically treating the obtained mixture for 4 hours, evaporating ethanol, and drying in vacuum at room temperature to obtain a solid which is recorded as a nano platinum precursor.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 4.
Steps (6) and (7) are the same as steps (6) and (7) of example 1, respectively.
The test results are listed in the following table:
example 8
Steps (1) and (2) are the same as steps (1) and (2) of example 1, respectively.
(3) 500mg of the above rGO/Co3Ni1/C-N@SiO2The solid was mixed with 50 mL of absolute ethanol, sonicated to uniformly disperse the solid, and then 25 mg of trimethyl platinum iodide (C) was added3H9IPt), ultrasonically treating the obtained mixture for 4 hours, evaporating ethanol, and drying in vacuum at room temperature to obtain a solid which is recorded as a nano platinum precursor.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 4.
Steps (6) and (7) are the same as steps (6) and (7) of example 1, respectively.
The test results are listed in the following table:
。
Claims (5)
1. a preparation method of a carbon hollow sphere composite material with low platinum loading capacity is characterized by comprising the following steps:
(1) nickel cobalt doped polydopamine coated silica spheres (PDA-Co) were prepared according to a modified prior art (Wei Wu, Wei Zhang, Yu Long, et al, Journal of colloid and Interface Science 531 (2018) 642-653)3Ni1@SiO2）；
(2) The above PDA-Co3Ni1@SiO2500mg of solid was added to a concentration of 0.5 mg X mL-1The graphene oxide dispersion liquid is fully stirred and centrifuged, and the obtained solid is 40 percentoVacuum drying under C, then under nitrogen atmosphere, at 5oC×min-1The temperature is increased to 850 ℃, then the constant temperature is kept for a certain time, the mixture is naturally cooled to the room temperature, and the obtained solid is recorded as rGO/Co3Ni1/C-N@SiO2；
(3) Mixing the above rGO/Co3Ni1/C-N@SiO2Mixing the solid with absolute ethyl alcohol, performing ultrasonic treatment to uniformly disperse the solid, then adding a platinum compound, performing ultrasonic treatment on the obtained mixture, evaporating the ethyl alcohol, and performing vacuum drying at room temperature to obtain the solid as a nano platinum precursor; rGO/Co in mixed solution3Ni1/C-N@SiO2The mass ratio to the platinum compound is 50: 1 ~ 5;
(4) ultrasonically dispersing the nano platinum precursor in formamide, heating to 135 ℃, performing a reflux reaction, centrifuging, and recording the obtained solid as Pt/rGO/Co3Ni1/C-N@SiO2；
(5) Ultrasonically dispersing soluble starch and dicyandiamide in absolute ethyl alcohol, and then adding the Pt/rGO/Co3Ni1/C-N@SiO2Performing ultrasonic treatment, and finally evaporating ethanol to obtain a solid mixture which is recorded as a catalyst precursor; the soluble starch is dicyandiamide Pt/rGO/Co3Ni1/C-N@SiO2The mass ratio of (1: 10), (20 ~ 60);
(6) the catalyst precursor was reacted in a nitrogen atmosphere at a temperature of 4 deg.CoC×min-1Is heated to 800 DEG CThen keeping the temperature constant for a certain time, naturally cooling to room temperature, and soaking the obtained black powder in 4 mol × L-1After slowly stirring thoroughly at room temperature, the resulting solution was centrifuged, washed with water to neutrality, and the resultant solution was dissolved in KOH solution (50)oAnd C, vacuum drying is carried out, and the obtained black powder is the carbon hollow sphere composite material with low platinum loading.
2. The method for preparing the carbon hollow sphere composite material with low platinum loading according to claim 1, wherein in the step (3), the platinum compound is chloroplatinic acid (H)2PtCl6×6H2O), or platinum chloride (PtCl)4) Or trimethylmethylcyclopentadienyl platinum (C)9H16Pt), or trimethyl platinum iodide (C)3H9IPt）C3H9IPt）。
3. The method for preparing the carbon hollow sphere composite material with low platinum loading as claimed in claim 1, wherein in the step (1), the silica spheres with a diameter of 360-380 nm are prepared, i.e. ethyl orthosilicate is slowly dripped into a mixed solution consisting of ethanol, water and ammonia water containing 25wt% of ammonia under continuous stirring, after dripping, uniform stirring is continuously carried out, the obtained solid is centrifugally separated, and the water and the ethanol are sequentially washed for multiple times, namely 50 timesoVacuum drying is carried out under C to obtain silicon dioxide balls; the volume ratio of ethyl orthosilicate, ethanol, water and ammonia water containing 25wt% of ammonia is 20: 250: 100: 13;
then, ultrasonically dispersing the silicon dioxide spheres in water to form uniform dispersion liquid; followed by the addition of NiCl2×6H2O and CoCl2×6H2Continuously performing ultrasonic treatment, adding dopamine after the dopamine is completely dissolved, and continuously performing ultrasonic treatment to completely dissolve the dopamine; adding under stirring tris (hydroxymethyl) methylamine, stirring the solution at constant speed thoroughly, centrifuging, washing the obtained solid with water, 40%oVacuum drying under C to obtain PDA-Co3Ni1@SiO2。
4. A low platinum loading carbon hollow sphere composite material prepared according to the method of claim 1.
5. Use of a low platinum loading carbon hollow sphere composite material prepared according to the method of claim 1 in electrocatalysis of oxygen reduction reactions.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI243507B (en) * | 2004-12-30 | 2005-11-11 | Ind Tech Res Inst | Hollow mesocarbon electrode-catalyst for direct methanol fuel cell and preparation thereof |
| CN102294239A (en) * | 2011-06-02 | 2011-12-28 | 湖南科技大学 | Metal nano electro-catalyst for redox reaction of fuel cell, and preparation method and application thereof |
| US20130215184A1 (en) * | 2012-02-17 | 2013-08-22 | International Paper Company | Absorbent plastic pigment with improved print density and recording sheet containing same |
| CN103928691A (en) * | 2014-04-10 | 2014-07-16 | 哈尔滨工业大学 | Platinum-based catalyst carrier of direct methanol fuel cell and preparation method thereof |
| CN107051566A (en) * | 2017-03-22 | 2017-08-18 | 湖北大学 | The method that the preparation method of azepine carbon coating cobalt catalyst and unsaturated compound based on above-mentioned catalyst are catalyzed transfer hydrogenation |
| CN109126858A (en) * | 2018-11-05 | 2019-01-04 | 湖南科技大学 | Preparation method of bifunctional catalyst that is a kind of while generating diglycolic acid and hydrogen and products thereof and application |
| KR20190009584A (en) * | 2017-07-19 | 2019-01-29 | 한국과학기술원 | Catalyst for fuel cell and method of manufacturing the same, and membrane-electrode assmbly and method of manufacturing the same |
| CN110028053A (en) * | 2019-05-16 | 2019-07-19 | 济宁医学院 | A kind of preparation method and applications of high nitrogen doped amount nano cages material |
-
2019
- 2019-10-23 CN CN201911013855.7A patent/CN110690463B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI243507B (en) * | 2004-12-30 | 2005-11-11 | Ind Tech Res Inst | Hollow mesocarbon electrode-catalyst for direct methanol fuel cell and preparation thereof |
| CN102294239A (en) * | 2011-06-02 | 2011-12-28 | 湖南科技大学 | Metal nano electro-catalyst for redox reaction of fuel cell, and preparation method and application thereof |
| US20130215184A1 (en) * | 2012-02-17 | 2013-08-22 | International Paper Company | Absorbent plastic pigment with improved print density and recording sheet containing same |
| CN103928691A (en) * | 2014-04-10 | 2014-07-16 | 哈尔滨工业大学 | Platinum-based catalyst carrier of direct methanol fuel cell and preparation method thereof |
| CN107051566A (en) * | 2017-03-22 | 2017-08-18 | 湖北大学 | The method that the preparation method of azepine carbon coating cobalt catalyst and unsaturated compound based on above-mentioned catalyst are catalyzed transfer hydrogenation |
| KR20190009584A (en) * | 2017-07-19 | 2019-01-29 | 한국과학기술원 | Catalyst for fuel cell and method of manufacturing the same, and membrane-electrode assmbly and method of manufacturing the same |
| CN109126858A (en) * | 2018-11-05 | 2019-01-04 | 湖南科技大学 | Preparation method of bifunctional catalyst that is a kind of while generating diglycolic acid and hydrogen and products thereof and application |
| CN110028053A (en) * | 2019-05-16 | 2019-07-19 | 济宁医学院 | A kind of preparation method and applications of high nitrogen doped amount nano cages material |
Non-Patent Citations (3)
| Title |
|---|
| WEI WU: "Ni modified Pd nanoparticles immobilized on hollow nitrogen doped carbon spheres for the simehydrogenation of phenylacetylene", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 石峰: "低铂—非金属复合催化剂的构筑和性能研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
| 郑亚荣: "基于廉价金属复合材料电催化剂设计、合成及性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111490257A (en) * | 2020-04-03 | 2020-08-04 | 三峡大学 | Preparation method of bifunctional Co-N-C electrocatalyst |
| CN113078330A (en) * | 2021-04-09 | 2021-07-06 | 湖南科技大学 | Porous carbon-doped platinum-supported catalyst and preparation and application thereof |
| CN113078330B (en) * | 2021-04-09 | 2022-04-22 | 湖南科技大学 | Porous carbon-doped platinum-supported catalyst and preparation and application thereof |
| CN113106491A (en) * | 2021-04-30 | 2021-07-13 | 佛山仙湖实验室 | Preparation method of nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material, product and application thereof |
| CN116099566A (en) * | 2023-01-09 | 2023-05-12 | 三峡大学 | Preparation method of platinum doped modified cobalt-based catalyst |
| CN117976926A (en) * | 2024-03-28 | 2024-05-03 | 上海唐锋能源科技有限公司 | Preparation method of durable Pt-M alloy catalyst |
| CN117976926B (en) * | 2024-03-28 | 2024-06-04 | 上海唐锋能源科技有限公司 | Preparation method of durable Pt-M alloy catalyst |
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