CN113106491B - Preparation method of nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material, product and application thereof - Google Patents
Preparation method of nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material, product and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalytic material, which comprises the following steps: (1) preparing nitrogen-doped carbon-coated silicon dioxide spheres; (2) preparing nitrogen-doped hollow carbon spheres; (3) preparing activated nitrogen-doped mesoporous hollow carbon spheres; (4) preparing the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material. The nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material provided by the invention greatly reduces the loading capacity of platinum through the electron transfer and synergistic effect of platinum nanoparticles and cobaltosic oxide, and the loading capacity of the noble metal platinum of the composite electro-catalytic material is only 1/19 of commercial platinum carbon, so that the material cost is greatly reduced, and meanwhile, the composite electro-catalytic material has more excellent hydrogen evolution activity.
Description
Technical Field
The invention relates to the field of electrochemical energy materials, in particular to a preparation method of a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalytic material, and a product and application thereof.
Background
With the increasingly prominent problems of environmental pollution and energy shortage, the development of clean new energy sources and the efficient utilization of renewable energy sources such as solar energy, wind energy, hydrogen energy and the like become more urgent. Among them, hydrogen has a high combustion heat value, and the product is only water, which is a very interesting clean energy. The hydrogen production technology by electrocatalysis water decomposition not only realizes green conversion from electric energy to chemical energy, but also has high purity and strong reproducibility of the prepared hydrogen. The key of the electrocatalytic decomposition water evolution hydrogen reaction is to prepare an electrocatalyst with high efficiency, low cost and long service life, the best performance is the electrocatalyst mainly based on noble metal platinum (Pt) at present, but the wide application of the electrocatalyst is severely limited by the rare reserve and high price of platinum, so that the research and development of the high-efficiency hydrogen evolution electrocatalyst with low price and excellent performance are very important.
In recent years, work on non-noble metal-based electrocatalysts has also been rapidly developed, but the performance of the electrocatalysts has not reached the requirements of large-scale application to date, and is mainly related to the poor catalytic kinetics of the non-noble metal-based electrocatalysts. The problem is effectively solved by combining the noble metal and the non-noble metal oxide into a composite system through strong metal carrier interaction, the aggregation of metal particles can be effectively prevented through electron transfer and chemical interaction generated between the noble metal and the non-noble metal oxide, so that the stability of the catalyst is improved, the energy barrier of hydrogen migration is reduced, meanwhile, the loading capacity of the noble metal is greatly reduced, and the economic cost is reduced. The platinum-cobalt oxide composite electrocatalytic material loaded on the nitrogen-doped mesoporous hollow carbon spheres and the preparation method thereof are provided, the loading capacity of platinum is reduced by electron transfer and synergistic effect between noble metal and non-noble metal oxide, and the electrocatalytic material has excellent hydrogen evolution activity, simple synthetic process and convenient operation.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides a preparation method of a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalysis material, and a product and an application thereof.
The invention aims to provide a preparation method of a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalytic material, which comprises the following steps:
(1) preparing nitrogen-doped carbon-coated silica spheres: sequentially dissolving tetraethoxysilane, ethanol and ammonia water in deionized water, stirring, adding a dopamine solution to obtain a composite solution, fully stirring the composite solution to form polydopamine-coated silicon dioxide spheres with uniform sizes, and performing high-temperature carbonization treatment to obtain nitrogen-doped carbon-coated silicon dioxide spheres;
(2) preparing nitrogen-doped hollow carbon spheres: adding the nitrogen-doped carbon-coated silicon dioxide spheres obtained in the step (1) into a hydrofluoric acid solution, fully stirring the obtained solution to remove a silicon dioxide template, and then centrifugally washing and drying to obtain nitrogen-doped hollow carbon spheres;
(3) preparing activated nitrogen-doped mesoporous hollow carbon spheres: mixing a chemical activating agent with the nitrogen-doped hollow carbon spheres obtained in the step (2) according to a certain mass ratio, placing the mixture in a tubular furnace for high-temperature calcination, washing the obtained product to be neutral, and drying to obtain activated nitrogen-doped mesoporous hollow carbon spheres with ultrahigh specific surface area and mesoporous structures;
(4) preparing a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material: and (3) uniformly dispersing the activated nitrogen-doped mesoporous hollow carbon spheres obtained in the step (3) in an ethylene glycol solvent, sequentially adding a chloroplatinic acid solution and a cobalt salt, performing sufficient magnetic stirring, then putting the mixture into an oil bath pot, heating and stirring, slowly and dropwise adding a sodium borohydride solution under vigorous stirring to prevent the reduced platinum metal nanoparticles from aggregating, and then centrifugally washing and drying the obtained product to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalytic material.
Preferably, the mass ratio of tetraethyl orthosilicate, ammonia water and ethanol in the step (1) is 1-3: 1-3: 10-15, wherein the concentration of the dopamine solution is 40-60mg/ml, and the mass concentration of the dopamine solution in the composite solution is 1-5 wt%.
Preferably, the hydrofluoric acid mass concentration in the step (2) is 10 wt% to 20 wt%.
Preferably, the chemical activator in step (3) is potassium hydroxide, and the high-temperature calcination temperature is 700-. When the activation temperature reaches 700-900 ℃, the potassium compound is reduced to potassium vapor by carbon (2KOH → K)2O+H2O，K2O + C → 2K + CO), part of the potassium vapor will be embedded in the carbon skeleton, widening the atomic layer of carbon, and the potassium and potassium compounds will be subsequently coatedAnd removing the carbon spheres to form an ultra-high specific surface area and pore structure. The high specific surface area and the mesoporous structure are beneficial to improving the surface active sites of the catalyst and improving the utilization rate and the real surface area of the catalyst, thereby achieving the purposes of improving the hydrogen evolution performance and reducing the cost of the catalyst.
Further preferably, the mass ratio of the potassium hydroxide to the nitrogen-doped hollow carbon spheres is 10: 1-1: 1.
preferably, the platinum metal content of the chloroplatinic acid solution in step (4) is 0 to 10 wt%, and the cobalt metal content of the cobalt salt is 0 to 10 wt%.
More preferably, the cobalt salt is selected from any one of cobalt acetate tetrahydrate, cobalt chloride and cobalt nitrate.
Preferably, the magnetic stirring time in the step (4) is 1-3 hours, the temperature of the oil bath is set to be 100-140 ℃, and the mass of the sodium borohydride is 20-30 wt%.
The invention also aims to provide the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electrocatalytic material prepared by the preparation method of the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electrocatalytic material.
The invention also protects the application of the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electro-catalysis material in the aspect of water electrolysis catalyst materials.
Preferably, the application of the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electrocatalytic material is to perform electrocatalytic decomposition on water to prepare hydrogen at room temperature and under the condition of a sulfuric acid solution with 0.5mol/L electrolyte.
Compared with the prior art, the invention has the following advantages:
1. the hollow carbon spheres activated by the chemical activator KOH have an ultra-high specific surface area, and the hollow carbon spheres are used as a substrate to load the platinum-cobalt oxide composite electrocatalytic material, so that the dispersibility of carbon-supported metal is facilitated (as shown in figures 1 and 2).
2. The 1.05 wt.% platinum loading of the composite catalyst has better electrocatalytic performance than the 20 wt.% platinum loading of the commercial Pt/C (as shown in fig. 5 and 6) by electron transfer and synergistic effects between the platinum nanoparticles and the cobaltosic oxide.
3. The preparation method does not need long-time hydrothermal reaction and subsequent calcining process, has simple synthetic process, convenient operation, short reaction time, reliable repeatability, no need of high-temperature heat treatment in the later period and low production cost, and is very suitable for large-scale industrial production.
Drawings
Fig. 1 is a scanning electron microscope picture of activated nitrogen-doped mesoporous hollow carbon spheres prepared in example 1 of the present invention;
fig. 2 is a specific surface area diagram of a nitrogen-doped mesoporous hollow carbon sphere prepared in example 1 of the present invention, wherein (a) is before activation, and (b) is after activation;
FIG. 3 shows a scanning electron microscope image and a transmission electron microscope image of the composite electro-catalytic material prepared in example 1 of the present invention, wherein (a) is the scanning electron microscope image, and (b) is the transmission electron microscope image;
FIG. 4 is an X-ray diffraction pattern of a composite electrocatalytic material prepared in example 1 of the present invention;
FIG. 5 is a graph comparing the hydrogen evolution reactivity of comparative examples 1, 2 and 20 wt.% of commercial platinum carbon according to the present invention with that of the composite electrocatalytic material prepared in this example 1;
FIG. 6 is a graph comparing hydrogen evolution reactivity of composite electrocatalytic materials prepared in examples 1-4 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
Comparative example 1
(1) Preparing nitrogen-doped carbon-coated silica spheres: 1869mg of tetraethyl orthosilicate, 23670mg of ethanol and 1820mg of ammonia water are added into 100000mg of deionized water, 500mg of dopamine solution is added after stirring for 30 minutes to obtain a composite solution, and the composite solution is placed on a magnetic stirrer and stirred for 48 hours to form the polydopamine-coated silicon dioxide spheres with uniform size. And (3) placing the collected polydopamine-coated silicon dioxide spheres in a tubular furnace, heating to 700 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours to obtain the nitrogen-doped carbon-coated silicon dioxide spheres.
(2) Preparing nitrogen-doped hollow carbon spheres: adding the nitrogen-doped carbon-coated silicon dioxide spheres obtained in the step (1) into a 10 wt% hydrofluoric acid solution, stirring for 2 hours to remove a silicon dioxide template, washing, centrifuging and drying to obtain nitrogen-doped hollow carbon spheres;
(3) preparing activated nitrogen-doped mesoporous hollow carbon spheres: mixing a chemical activating agent KOH and the nitrogen-doped hollow carbon spheres according to the mass ratio of 6: 1 (3 g of potassium hydroxide, 500mg of nitrogen-doped mesoporous hollow carbon spheres), placing the mixture in a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours. And washing the obtained product to be neutral by using water to remove potassium and potassium compounds, and drying to obtain the nitrogen-doped mesoporous hollow carbon spheres with ultrahigh specific surface area and mesoporous structure.
(4) Preparing a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material: and (2) uniformly dispersing 50mg of activated nitrogen-doped mesoporous hollow carbon spheres in 100mL of ethylene glycol solvent, adding 10% of platinum by theoretical mass fraction, placing the mixture on a magnetic stirrer to stir for 2 hours, then placing the mixture into an oil bath pot to be heated and stirred, then adding 200mg of sodium borohydride solution, reacting for 1 hour, centrifuging, washing and drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalytic material.
Comparative example 2
(1) Preparing nitrogen-doped carbon-coated silica spheres: 1869mg of tetraethyl orthosilicate, 23670mg of ethanol and 1820mg of ammonia water are added into 100000mg of deionized water, 500mg of dopamine solution is added after stirring for 30 minutes to obtain a composite solution, and the composite solution is placed on a magnetic stirrer and stirred for 48 hours to form the polydopamine-coated silicon dioxide spheres with uniform size. And (3) placing the collected polydopamine-coated silicon dioxide spheres in a tubular furnace, heating to 700 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours to obtain the nitrogen-doped carbon-coated silicon dioxide spheres.
(2) Preparing nitrogen-doped hollow carbon spheres: adding the nitrogen-doped carbon-coated silicon dioxide spheres obtained in the step (1) into a 10 wt% hydrofluoric acid solution, stirring for 2 hours to remove a silicon dioxide template, washing, centrifuging and drying to obtain nitrogen-doped hollow carbon spheres;
(3) preparing activated nitrogen-doped mesoporous hollow carbon spheres: mixing a chemical activating agent KOH and the nitrogen-doped hollow carbon spheres according to the mass ratio of 6: 1 (3 g of potassium hydroxide, 500mg of nitrogen-doped mesoporous hollow carbon spheres), placing the mixture in a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours. And washing the obtained product to be neutral by using water to remove potassium and potassium compounds, and drying to obtain the nitrogen-doped mesoporous hollow carbon spheres with ultrahigh specific surface area and mesoporous structure.
(4) Preparing a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material: and (2) uniformly dispersing 50mg of activated nitrogen-doped mesoporous hollow carbon spheres in 100mL of ethylene glycol solvent, adding 10% of cobalt by theoretical mass fraction, placing the mixture on a magnetic stirrer to stir for 2 hours, then placing the mixture into an oil bath pot to be heated and stirred, then adding 200mg of sodium borohydride solution, reacting for 1 hour, centrifuging, washing and drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalytic material.
Example 1
(1) Preparing nitrogen-doped carbon-coated silica spheres: 1869mg of tetraethoxysilane, 23670mg of ethanol and 1820mg of ammonia water are added into 100000mg of deionized water, 500mg of dopamine solution is added after stirring for 30 minutes to obtain a composite solution, and the composite solution is placed on a magnetic stirrer to be stirred for 48 hours to form the polydopamine-coated silicon dioxide spheres with uniform sizes. And (3) placing the collected polydopamine-coated silicon dioxide spheres in a tubular furnace, heating to 700 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours to obtain the nitrogen-doped carbon-coated silicon dioxide spheres.
(2) Preparing nitrogen-doped hollow carbon spheres: adding the nitrogen-doped carbon-coated silicon dioxide spheres obtained in the step (1) into a 10 wt% hydrofluoric acid solution, stirring for 2 hours to remove a silicon dioxide template, washing, centrifuging and drying to obtain nitrogen-doped hollow carbon spheres;
(3) preparing activated nitrogen-doped mesoporous hollow carbon spheres: mixing a chemical activating agent KOH and the nitrogen-doped hollow carbon spheres according to the mass ratio of 6: 1 (3 g of potassium hydroxide, 500mg of nitrogen-doped mesoporous hollow carbon spheres), placing the mixture in a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours. And washing the obtained product to be neutral by using water to remove potassium and potassium compounds, and drying to obtain the nitrogen-doped hollow carbon spheres with ultrahigh specific surface area and mesoporous structure.
(4) Preparing a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material: and (2) uniformly dispersing 50mg of activated nitrogen-doped mesoporous hollow carbon spheres in 100mL of ethylene glycol solvent, adding platinum with the theoretical mass fraction of 2.5% and cobalt with the theoretical mass fraction of 7.5%, placing the mixture on a magnetic stirrer to stir for 2 hours, then placing the mixture in an oil bath pot to be heated and stirred, then adding 200mg of sodium borohydride solution, reacting for 1 hour, centrifuging, washing and drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalysis material.
Fig. 1 is a scanning electron micrograph of the activated nitrogen-doped mesoporous hollow carbon spheres prepared in example 1, which shows that the carbon spheres have a hollow structure and the surface of the activated carbon spheres has a very obvious pore structure,
fig. 2 is a comparison graph of specific surface area of the carbon spheres before and after activation in example 1, and the specific surface area of the carbon spheres after activation is up to 1339m2/g, which is 2.6 times that of the carbon spheres before activation.
Fig. 3 is a scanning electron microscope and a transmission electron microscope photo of the nitrogen-doped mesoporous hollow carbon sphere-supported platinum-cobalt oxide composite electro-catalytic material prepared in this embodiment 1, in which cobalt salt is reduced to cobalt oxide nano-sheets to coat the surfaces of the carbon spheres, and platinum is reduced to metal platinum nano-particles anchored on the carbon spheres and the cobalt oxide nano-sheets.
FIG. 4 is an X-ray diffraction pattern of example 1, from which it can be seen that (111), (311), (511) crystal planes of cobalt oxide are present in the composite material, confirming the presence of cobalt oxide in the composite electrocatalyst, no diffraction peak is formed due to the lower loading of Pt. The theoretical amounts of platinum and cobalt added in this example were 2.5 wt.% and 7.5 wt.%, respectively, and the actual amounts of platinum and cobalt were 1.05 wt.% and 3.29 wt.% after full spectrum direct read plasma emission spectrometer testing. In the catalyst, because the loading amount of platinum is low, the improvement of hydrogen evolution performance is mainly due to electron transfer and synergistic effect between platinum nanoparticles and cobaltosic oxide.
Fig. 5 is a graph comparing the hydrogen evolution reactivity of the composite electrocatalysts measured under the standard three-electrode system for the commercial platinum carbon of example 1, comparative example 2 and 20 wt.%, and it can be found that the nitrogen-doped mesoporous hollow carbon sphere-supported platinum-cobalt oxide composite electrocatalysts prepared in example 1 exhibit more excellent hydrogen evolution performance than the commercial platinum carbon with the loading of Pt of 20 wt.%.
Example 2
(1) Preparing nitrogen-doped carbon-coated silica spheres: 1869mg of tetraethyl orthosilicate, 23670mg of ethanol and 1820mg of ammonia water are added into 100000mg of deionized water, 500mg of dopamine solution is added after stirring for 30 minutes to obtain a composite solution, and the composite solution is placed on a magnetic stirrer and stirred for 48 hours to form the polydopamine-coated silicon dioxide spheres with uniform size. And (3) placing the collected polydopamine-coated silicon dioxide spheres in a tubular furnace, heating to 700 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours to obtain the nitrogen-doped carbon-coated silicon dioxide spheres.
(2) Preparing nitrogen-doped hollow carbon spheres: adding the nitrogen-doped carbon-coated silicon dioxide spheres obtained in the step (1) into a 10 wt% hydrofluoric acid solution, stirring for 2 hours to remove a silicon dioxide template, washing, centrifuging and drying to obtain nitrogen-doped hollow carbon spheres;
(3) preparing activated nitrogen-doped mesoporous hollow carbon spheres: mixing a chemical activating agent KOH and the nitrogen-doped hollow carbon spheres according to the mass ratio of 6: 1 (3 g of potassium hydroxide, 500mg of nitrogen-doped mesoporous hollow carbon spheres), placing the mixture in a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours. And washing the obtained product to be neutral by using water to remove potassium and potassium compounds, and drying to obtain the nitrogen-doped mesoporous hollow carbon spheres with ultrahigh specific surface area and mesoporous structure.
(4) Preparing a composite electro-catalytic material with ultralow load of platinum-cobalt oxide anchored on a nitrogen-doped mesoporous hollow carbon sphere: and (2) uniformly dispersing 50mg of activated nitrogen-doped mesoporous hollow carbon spheres in 100mL of ethylene glycol solvent, adding 4.5% of platinum by theoretical mass fraction and 5.5% of cobalt by theoretical mass fraction, placing the mixture on a magnetic stirrer to stir for 2 hours, then placing the mixture in an oil bath pot to be heated and stirred, then adding 200mg of sodium borohydride solution, reacting for 1 hour, centrifuging, washing and drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalysis material.
Example 3
(1) Preparing nitrogen-doped carbon-coated silica spheres: 1869mg of tetraethyl orthosilicate, 23670mg of ethanol and 1820mg of ammonia water are added into 100000mg of deionized water, 500mg of dopamine solution is added after stirring for 30 minutes to obtain a composite solution, and the composite solution is placed on a magnetic stirrer and stirred for 48 hours to form the polydopamine-coated silicon dioxide spheres with uniform size. And (3) placing the collected polydopamine-coated silicon dioxide spheres in a tubular furnace, heating to 700 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours to obtain the nitrogen-doped carbon-coated silicon dioxide spheres.
(2) Preparing nitrogen-doped hollow carbon spheres: adding the nitrogen-doped carbon-coated silicon dioxide spheres obtained in the step (1) into a 10 wt% hydrofluoric acid solution, stirring for 2 hours to remove a silicon dioxide template, washing, centrifuging and drying to obtain nitrogen-doped hollow carbon spheres;
(3) preparing activated nitrogen-doped mesoporous hollow carbon spheres: mixing a chemical activating agent KOH and the nitrogen-doped hollow carbon spheres according to the mass ratio of 6: 1 (3 g of potassium hydroxide, 500mg of nitrogen-doped mesoporous hollow carbon spheres), placing the mixture in a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours. And washing the obtained product to be neutral by using water to remove potassium and potassium compounds, and drying to obtain the nitrogen-doped mesoporous hollow carbon spheres with ultrahigh specific surface area and mesoporous structure.
(4) Preparing a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material: and (2) uniformly dispersing 50mg of activated nitrogen-doped mesoporous hollow carbon spheres in 100mL of ethylene glycol solvent, adding platinum with the theoretical mass fraction of 6.5% and cobalt with the theoretical mass fraction of 3.5%, placing the mixture on a magnetic stirrer to stir for 2 hours, then placing the mixture in an oil bath pot to be heated and stirred, then adding 200mg of sodium borohydride solution, reacting for 1 hour, centrifuging, washing and drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalysis material.
Example 4
(1) Preparing nitrogen-doped carbon-coated silica spheres: 1869mg of tetraethyl orthosilicate, 23670mg of ethanol and 1820mg of ammonia water are added into 100000mg of deionized water, 500mg of dopamine solution is added after stirring for 30 minutes to obtain a composite solution, and the composite solution is placed on a magnetic stirrer and stirred for 48 hours to form the polydopamine-coated silicon dioxide spheres with uniform size. And (3) placing the collected polydopamine-coated silicon dioxide spheres in a tubular furnace, heating to 700 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours to obtain the nitrogen-doped carbon-coated silicon dioxide spheres.
(2) Preparing nitrogen-doped hollow carbon spheres: adding the nitrogen-doped carbon-coated silicon dioxide spheres obtained in the step (1) into a 10 wt% hydrofluoric acid solution, stirring for 2 hours to remove a silicon dioxide template, washing, centrifuging and drying to obtain nitrogen-doped hollow carbon spheres;
(3) preparing activated nitrogen-doped mesoporous hollow carbon spheres: mixing a chemical activating agent KOH and the nitrogen-doped hollow carbon spheres according to the mass ratio of 6: 1 (3 g of potassium hydroxide, 500mg of nitrogen-doped mesoporous hollow carbon spheres), placing the mixture in a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours. And washing the obtained product to be neutral by using water to remove potassium and potassium compounds, and drying to obtain the nitrogen-doped mesoporous hollow carbon spheres with ultrahigh specific surface area and mesoporous structure.
(4) Preparing a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material: and (2) uniformly dispersing 50mg of activated nitrogen-doped mesoporous hollow carbon spheres in 100mL of ethylene glycol solvent, adding 8.5% of platinum by theoretical mass fraction and 1.5% of cobalt by theoretical mass fraction, placing the mixture on a magnetic stirrer to stir for 2 hours, then placing the mixture in an oil bath pot to be heated and stirred, then adding 200mg of sodium borohydride solution, reacting for 1 hour, centrifuging, washing and drying to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalysis material.
The hydrogen evolution reaction activity test of the nitrogen-doped mesoporous hollow carbon sphere-supported platinum-cobalt oxide composite electrocatalytic material prepared in the examples 1 to 4 is performed, the result is shown in fig. 6, a comparison graph of the hydrogen evolution reaction activity of the composite electrocatalytic material measured under a standard three-electrode system shows that the Pt and Co with different contents loaded by the method can obtain excellent performance, and the hydrogen evolution reaction activity performance of the nitrogen-doped mesoporous hollow carbon sphere-supported platinum-cobalt oxide composite electrocatalytic material prepared in the example 1 is optimal.
Example 5
(1) Preparing nitrogen-doped carbon-coated silica spheres: 1869mg of tetraethyl orthosilicate, 23670mg of ethanol and 1820mg of ammonia water are added into 100000mg of deionized water, 500mg of dopamine solution is added after stirring for 30 minutes to obtain a composite solution, and the composite solution is placed on a magnetic stirrer and stirred for 48 hours to form the polydopamine-coated silicon dioxide spheres with uniform size. And (3) placing the collected polydopamine-coated silicon dioxide spheres in a tubular furnace, heating to 700 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours to obtain the nitrogen-doped carbon-coated silicon dioxide spheres.
(2) Preparing nitrogen-doped hollow carbon spheres: adding the nitrogen-doped carbon-coated silicon dioxide spheres obtained in the step (1) into a 10 wt% hydrofluoric acid solution, stirring for 2 hours to remove a silicon dioxide template, washing, centrifuging and drying to obtain nitrogen-doped hollow carbon spheres;
(3) preparing activated nitrogen-doped mesoporous hollow carbon spheres: mixing a chemical activator KOH and the nitrogen-doped hollow carbon spheres according to the mass ratio of 10: 1 (5 g of potassium hydroxide, 500mg of nitrogen-doped mesoporous hollow carbon spheres), placing the mixture in a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours. And washing the obtained product to be neutral by using water to remove potassium and potassium compounds, and drying to obtain the nitrogen-doped mesoporous hollow carbon spheres with ultrahigh specific surface area and mesoporous structure.
(4) Preparing a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material: and (2) uniformly dispersing 50mg of activated nitrogen-doped mesoporous hollow carbon spheres in 100mL of ethylene glycol solvent, adding 1.5% of platinum by theoretical mass fraction and 8.5% of cobalt by theoretical mass fraction, placing the mixture on a magnetic stirrer, stirring the mixture for 2 hours, placing the mixture in an oil bath pot, heating and stirring the mixture, then adding 200mg of sodium borohydride solution, reacting for 1 hour, centrifuging, washing and drying the product to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalysis material.
Example 6
(1) Preparing nitrogen-doped carbon-coated silica spheres: 1869mg of tetraethyl orthosilicate, 23670mg of ethanol and 1820mg of ammonia water are added into 100000mg of deionized water, 500mg of dopamine solution is added after stirring for 30 minutes to obtain a composite solution, and the composite solution is placed on a magnetic stirrer and stirred for 48 hours to form the polydopamine-coated silicon dioxide spheres with uniform size. And (3) placing the collected polydopamine-coated silicon dioxide spheres in a tubular furnace, heating to 700 ℃ at the speed of 10 ℃/min, and preserving heat for 2 hours to obtain the nitrogen-doped carbon-coated silicon dioxide spheres.
(2) Preparing nitrogen-doped hollow carbon spheres: adding the nitrogen-doped carbon-coated silicon dioxide spheres obtained in the step (1) into a 10 wt% hydrofluoric acid solution, stirring for 2 hours to remove a silicon dioxide template, washing, centrifuging and drying to obtain nitrogen-doped hollow carbon spheres;
(3) preparing activated nitrogen-doped mesoporous hollow carbon spheres: mixing a chemical activating agent KOH and the nitrogen-doped hollow carbon spheres according to the mass ratio of 2: 1 (1 g of potassium hydroxide, 500mg of nitrogen-doped mesoporous hollow carbon spheres), placing the mixture in a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours. And washing the obtained product to be neutral by using water to remove potassium and potassium compounds, and drying to obtain the nitrogen-doped mesoporous hollow carbon spheres with ultrahigh specific surface area and mesoporous structure.
(4) Preparing a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material: and (2) uniformly dispersing 50mg of activated nitrogen-doped mesoporous hollow carbon spheres in 100mL of ethylene glycol solvent, adding 1.5% of platinum by theoretical mass fraction and 8.5% of cobalt by theoretical mass fraction, placing the mixture on a magnetic stirrer, stirring the mixture for 2 hours, placing the mixture in an oil bath pot, heating and stirring the mixture, then adding 200mg of sodium borohydride solution, reacting for 1 hour, centrifuging, washing and drying the product to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalysis material.
The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing nitrogen-doped carbon-coated silica spheres: sequentially dissolving tetraethoxysilane, ethanol and ammonia water in deionized water, stirring, adding a dopamine solution to obtain a composite solution, fully stirring the composite solution to form polydopamine-coated silicon dioxide spheres, and carrying out high-temperature carbonization treatment to obtain nitrogen-doped carbon-coated silicon dioxide spheres;
(2) preparing nitrogen-doped hollow carbon spheres: adding the nitrogen-doped carbon-coated silicon dioxide spheres obtained in the step (1) into a hydrofluoric acid solution, and fully stirring, centrifugally washing and drying the obtained solution to obtain nitrogen-doped hollow carbon spheres;
(3) preparing activated nitrogen-doped mesoporous hollow carbon spheres: mixing a chemical activating agent with the nitrogen-doped hollow carbon spheres obtained in the step (2), then calcining at high temperature, washing the obtained product to be neutral, and drying to obtain activated nitrogen-doped mesoporous hollow carbon spheres with a mesoporous structure; the chemical activating agent is potassium hydroxide, and the high-temperature calcination temperature is 700-900 ℃;
(4) preparing a nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material: and (3) uniformly dispersing the activated nitrogen-doped mesoporous hollow carbon spheres obtained in the step (3) in an ethylene glycol solvent, sequentially adding a chloroplatinic acid solution and a cobalt salt, fully stirring, then putting the mixture into an oil bath pot, heating and stirring, dropwise adding a sodium borohydride solution under vigorous stirring, and then centrifugally washing and drying the obtained product to obtain the nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electrocatalytic material.
2. The preparation method of the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electrocatalytic material as claimed in claim 1, wherein the mass ratio of tetraethyl orthosilicate, ammonia water and ethanol in the step (1) is 1-3: 1-3: 10-15, wherein the concentration of the dopamine solution is 40-60mg/ml, and the mass concentration of the dopamine solution in the composite solution is 1-5 wt%.
3. The method for preparing the nitrogen-doped mesoporous hollow carbon sphere-supported platinum-cobalt oxide composite electrocatalytic material as claimed in claim 1, wherein the hydrofluoric acid in the step (2) has a mass concentration of 10 wt% -20 wt%.
4. The method for preparing the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electrocatalytic material as claimed in claim 1, wherein the mass ratio of the potassium hydroxide to the nitrogen-doped hollow carbon spheres is 10: 1-1: 1.
5. the method for preparing the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electrocatalytic material as claimed in claim 1, wherein the platinum metal content of the chloroplatinic acid solution in the step (4) is 0-10 wt%, the cobalt metal content of the cobalt salt is 0-10 wt%, and the cobalt salt is selected from any one of cobalt acetate tetrahydrate, cobalt chloride and cobalt nitrate.
6. The preparation method of the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electrocatalytic material as set forth in claim 1 or 5, wherein the stirring time in the step (4) is 1-3 hours, the temperature of the oil bath is set at 100-140 ℃, and the mass concentration of the sodium borohydride is 20-30 wt%.
7. The nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electrocatalytic material prepared by the preparation method of the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electrocatalytic material as recited in any one of claims 1 to 6.
8. The application of the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electro-catalytic material in the aspect of water electrolysis catalyst materials according to claim 7.
9. The application of the nitrogen-doped mesoporous hollow carbon sphere-loaded platinum-cobalt oxide composite electrocatalytic material as described in claim 8, wherein hydrogen is produced by electrocatalytic decomposition of water under the conditions of room temperature and 0.5mol/L sulfuric acid solution as electrolyte.
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| CN111470507A (en) * | 2019-01-23 | 2020-07-31 | 西北农林科技大学 | Preparation method of honeycomb-shaped carbon material, honeycomb-shaped carbon material prepared by preparation method and application of honeycomb-shaped carbon material |
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| CN112279236A (en) * | 2020-10-30 | 2021-01-29 | 中国科学院长春应用化学研究所 | Nitrogen-doped hollow carbon sphere and preparation method and application thereof |
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