CN114318411B - Cobalt/carbon nano tube/ruthenium electrocatalyst and preparation method and application thereof - Google Patents
Cobalt/carbon nano tube/ruthenium electrocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a cobalt/carbon nano tube/ruthenium electrocatalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: and (3) utilizing lysozyme to assist in cracking the cobalt-based zeolite imidazole ester skeleton precursor to obtain the bamboo-like carbon nanotube wrapping the cobalt nanoparticles, and further uniformly anchoring the ruthenium nanocluster to the surface of the bamboo-like carbon nanotube to obtain the cobalt/carbon nanotube/ruthenium composite material with the three-phase heterostructure. Compared with the prior art, the composite material has the advantages that due to the unique synergistic effect of the cobalt and ruthenium heterostructures respectively loaded on the inner and outer surfaces of the carbon tube and the components, more active sites are exposed, the charge/mass transmission performance is improved, and the adsorption energy to hydrogen is optimized, so that the cobalt/carbon nano tube/ruthenium composite material has excellent water analysis hydrogen reaction catalytic activity in the electrolyte with full pH and has higher stability. The composite material prepared by the invention has the advantages of low cost of raw materials, simple process and low reaction energy consumption.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a cobalt/carbon nano tube/ruthenium electrocatalyst, a preparation method and application thereof.
Background
With the increasing severity of environmental problems and the increasing shortage of energy, renewable energy storage and conversion technologies have become an important point of research in recent years. Hydrogen energy is considered to be an ideal energy carrier by virtue of high energy density, cleanliness, environmental protection, diversification of storage forms and the like. In the existing hydrogen production method, electrolytic water is extremely potential to produce hydrogen, especially, new energy sources such as solar energy, wind energy and the like are combined to serve as intermediate transition energy sources to convert electric energy to be supplied to an electrolytic water device, however, the thermodynamics and dynamics of hydrogen evolution reaction occurring on a cathode in the water electrolysis process are slower, and high overpotential is required in the process of the electrolytic water Hydrogen Evolution Reaction (HER). Therefore, there is a need to develop electrocatalysts with high catalytic activity and stability and low cost to improve the water electrolysis efficiency, providing a research basis for sustainable clean hydrogen energy for future development. Platinum is currently the most effective one of the electrocatalysts for hydrogen evolution reactions, but its wide application is severely hampered by the high cost due to the limited reserves of platinum in nature.
Accordingly, researchers have also conducted a great deal of research in order to find hydrogen evolution reaction electrocatalysts that replace platinum. Among them, the transition metal-carbon system is receiving a lot of attention because of its low cost and tunable electronic structure. However, the hydrogen evolution reactivity of the currently available transition metal-carbon systems is still relatively low, especially in acidic, basic and neutral full pH electrolytes, which are far less catalytically active than noble metal platinum carbon catalysts.
Disclosure of Invention
The invention aims to provide a cobalt/carbon nano tube/ruthenium electrocatalyst and a preparation method and application thereof, so as to solve the problems of low efficiency, narrow pH application range, low catalytic activity, poor stability, high cost and difficult industrial production.
The aim of the invention can be achieved by the following technical scheme:
a method for preparing cobalt/carbon nano tube/ruthenium electrocatalyst, comprising the following steps:
(1) Adding cobalt salt aqueous solution into lysozyme aqueous solution, uniformly mixing, adding dimethyl imidazole aqueous solution into the mixed solution, uniformly stirring, standing, separating and drying to obtain dimethyl imidazole cobalt salt/lysozyme;
(2) Heating and preserving the obtained dimethyl imidazole cobalt salt/lysozyme in inert gas to obtain cobalt/carbon nano tubes;
(3) Dispersing the obtained cobalt/carbon nano tube in a dispersing agent, sealing, heating and stirring, adding ruthenium salt, stirring overnight, separating and drying, heating and preserving heat in inert gas, and obtaining the cobalt/carbon nano tube/ruthenium electrocatalyst.
Further, in the step (1), cobalt salt in the cobalt salt aqueous solution is cobalt chloride, cobalt chloride hexahydrate, cobalt nitrate or cobalt nitrate hexahydrate, and the dosage ratio of the cobalt salt, lysozyme and dimethyl imidazole is (1-3 mmol) (100-300 mg) (0.07-0.2 mol).
Further, in the step (1), the concentration of the cobalt salt aqueous solution is 0.05-0.2 mol/L, the concentration of the lysozyme aqueous solution is 1-2 g/L, the concentration of the dimethyl imidazole aqueous solution is 1-3 mol/L, the standing temperature is room temperature, and the standing time is 20-30 h.
Further, in the step (2), the inert gas is nitrogen, the heating and heat preservation are divided into two sections, the first section heating temperature is 500-600 ℃, the heat preservation time is 2-4 h, the second section heating temperature is 850-950 ℃, and the heat preservation time is 2-4 h.
Further, in the step (3), the dispersing agent is absolute ethyl alcohol, the ruthenium salt is ruthenium chloride trihydrate, the dosage ratio of the cobalt/carbon nano tube to the dispersing agent to the ruthenium salt is (30-100 mg) (20-60 mL) (3-10 mg), the heating temperature is 50-70 ℃ in the heating and stirring process, the stirring rotating speed is 300-400 rpm, and the stirring time is 20-40 min.
Further, in the step (3), the inert gas is nitrogen, and in the heating and heat preservation process, the heating temperature is 650-750 ℃, and the heat preservation time is 2-4 hours.
The cobalt/carbon nano tube/ruthenium electrocatalyst is prepared by adopting the method.
The application of cobalt/carbon nano tube/ruthenium electrocatalyst is that the electrocatalyst is applied to catalyzing hydrogen evolution reaction in electrolyte.
Further, the application process specifically comprises the following steps: dispersing the electrocatalyst in a dispersing agent, loading the dispersing agent on a substrate electrode to serve as a working electrode, inserting a reference electrode and a counter electrode, applying voltage, and catalyzing hydrogen evolution in an alkaline solution, an acidic solution or a neutral solution saturated by inert gas.
Further, the dispersing agent is an ethanol solution containing perfluorosulfonic polymer, the substrate electrode is a glassy carbon electrode, the reference electrode is a calomel electrode, the counter electrode is a carbon rod, the inert gas is argon, the alkaline solution is a potassium hydroxide solution, the concentration of the alkaline solution is 0.4-2.0 mol/L, the acidic solution is a sulfuric acid solution, the concentration of the acidic solution is 0.2-1.0 mol/L, the neutral solution is a phosphate buffer salt solution, and the concentration of the neutral solution is 0.4-2.0 mol/L.
The invention utilizes lysozyme to assist the cleavage of cobalt-based zeolite imidazole ester skeleton precursor to obtain the bamboo-like carbon nanotube wrapped with Co nano particles, and further uniformly anchors Ru nano clusters to the surface of the bamboo-like Carbon Nanotube (CNT), thus obtaining the cobalt/carbon nanotube/ruthenium composite material with a three-phase heterostructure. The composite material is favorable for exposing more active sites, improving charge/mass transmission performance and optimizing adsorption energy to hydrogen due to the unique synergistic effect of cobalt and ruthenium heterostructures respectively loaded on the inner and outer surfaces of the carbon tube, so that the cobalt/carbon nano tube/ruthenium composite material has excellent water analysis hydrogen reaction catalytic activity in electrolyte with full pH and has stronger stability. The composite material obtained by the invention has strong conductivity, more active sites and better electrocatalytic activity than that of a platinum-carbon catalyst in acidic, alkaline and neutral electrolytes, and the preparation method has the advantages of low cost of raw materials, simple process and low reaction energy consumption, and is a novel efficient and economical preparation method of the electrocatalytic catalyst for hydrogen evolution reaction.
Compared with the prior art, the invention has the following characteristics:
(1) The extremely small amount of ruthenium nanoclusters in cobalt/carbon nano tubes/ruthenium are highly dispersed on the surface of the carbon nano tubes coated with cobalt, so that the number of catalytic active sites is greatly increased, the atom utilization rate is effectively improved, and meanwhile, the corrosion resistance of the catalyst in extreme pH is enhanced, so that the catalyst has excellent hydrogen evolution performance in the full pH range;
(2) The cobalt/carbon nano tube/ruthenium is a porous three-dimensional network structure composed of carbon nano tubes, and the structure is beneficial to exposing more catalytic active centers, simultaneously beneficial to electron transfer, high in conductivity and accelerating the transmission of electrons and protons in the hydrogen evolution reaction process;
(3) The cobalt/carbon nano tube/ruthenium has super strong coupling effect between the ruthenium nano cluster, the nitrogen doped carbon nano tube and the cobalt nano particle, and the active interface promotes the rearrangement of the electronic structure and transfers more electrons on the metal surface to the carbon layer, thereby optimizing the adsorption energy of hydrogen and improving the kinetics of hydrogen evolution reaction;
(4) The preparation raw materials only relate to common reagents such as cobalt salt, a very small amount of ruthenium chloride trihydrate, dimethyl imidazole, absolute ethyl alcohol and the like, and the preparation method has the advantages of low cost, high product purity, simple preparation process, good repeatability and easy industrial production.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of cobalt/carbon nanotubes/ruthenium prepared in example 1 of the present invention, wherein (a) is a low power SEM, and (b) is a high power SEM;
FIG. 2 is a Transmission Electron Microscope (TEM) of cobalt/carbon nanotubes/ruthenium prepared in example 1 of the present invention, wherein (a) is a low power transmission electron microscope, (b) is a high resolution transmission electron microscope, (c) is a partial enlarged view, and NPs represent nanoparticles;
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) of cobalt/carbon nanotube/ruthenium prepared in example 1 of the present invention;
FIG. 4 is a graph showing the linear sweep voltammogram of cobalt/carbon nanotubes/ruthenium prepared in example 1 of the present invention in a 1.0mol/L potassium hydroxide solution at a sweep rate of 5 mV/s;
FIG. 5 is a graph showing the linear sweep voltammogram of cobalt/carbon nanotubes/ruthenium prepared in example 1 of the present invention in a sulfuric acid solution at a sweep rate of 5mV/s of 0.5 mol/L;
FIG. 6 is a graph showing the linear sweep voltammogram of cobalt/carbon nanotubes/ruthenium prepared in example 1 of the present invention in a phosphate buffered saline solution at a sweep rate of 5mV/s of 1.0 mol/L.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
Example 1:
a method for preparing cobalt/carbon nano tube/ruthenium electrocatalyst, comprising the following steps:
(1) Dissolving 150mg of lysozyme into 90mL of aqueous solution to form a clear solution, then dripping the 15mL of aqueous solution of cobalt chloride hexahydrate dissolved with 364.771mg into the solution of lysozyme, uniformly mixing, adding 45mL of aqueous solution dissolved with 9.852g of dimethyl imidazole into the solution, uniformly stirring, standing at room temperature for 24 hours, and collecting a product through centrifugation and freeze drying to obtain dimethyl imidazole cobalt salt/lysozyme;
(2) Heating the obtained dimethyl imidazole cobalt salt/lysozyme to 550 ℃ in nitrogen and preserving heat for 3 hours, and then heating to 900 ℃ and preserving heat for 3 hours to obtain a cobalt/carbon nano tube;
(3) 50mg of the cobalt/carbon nanotube obtained above was weighed and dispersed in 30mL of absolute ethanol, sealed, heated to 60 ℃, stirred at 350rpm for 30min, then added with 5mg of ruthenium chloride trihydrate, kept vigorously stirred at 60 ℃ overnight, then centrifugally dried, heated to 700 ℃ in nitrogen, and kept for 3h to obtain cobalt/carbon nanotube/ruthenium.
In order to demonstrate the loading effect of the cobalt/carbon nanotube/ruthenium electrocatalyst prepared in this example, a scanning electron microscope, a transmission electron microscope and an X-ray photoelectron spectroscopy of the cobalt/carbon nanotube/ruthenium prepared in this example were photographed, and the results are shown in fig. 1, 2 and 3. Very little ruthenium nanoclusters in cobalt/carbon nano tube/ruthenium are highly dispersed on the surface of the carbon nano tube coated with cobalt, so that the number of catalytic active sites is greatly increased, and the atom utilization rate is effectively improved; cobalt/carbon nano tube/ruthenium is a porous three-dimensional network structure composed of carbon nano tubes, and the structure is beneficial to exposing more catalytic active centers, is beneficial to electron transfer, shows high conductivity, and accelerates the transmission of electrons and protons in the hydrogen evolution reaction process.
The cobalt/carbon nano tube/ruthenium electrocatalyst prepared in the embodiment is applied to the electrolyte to catalyze the hydrogen evolution reaction, and comprises the following steps: the prepared cobalt/carbon nano tube/ruthenium is dispersed in ethanol solution containing perfluorosulfonic polymer, then is loaded on a glassy carbon electrode to serve as a working electrode, a calomel electrode is used as a reference electrode, a carbon rod is used as a counter electrode, proper voltage is applied, and hydrogen evolution is catalyzed in 1.0mol/L potassium hydroxide solution, 0.5mol/L sulfuric acid solution and 1.0mol/L phosphate buffer salt solution which are saturated by argon.
To demonstrate the catalytic effect of the cobalt/carbon nanotube/ruthenium electrocatalyst prepared in this example, the linear sweep voltammograms of the cobalt/carbon nanotube/ruthenium prepared in this example in 1.0mol/L potassium hydroxide solution, 0.5mol/L sulfuric acid solution, and 1.0mol/L phosphate buffered saline solution at a sweep rate of 5mV/s were plotted, and the results are shown in FIGS. 4, 5, and 6. The cobalt/carbon nano tube/ruthenium has super strong coupling effect between the ruthenium nano cluster, the nitrogen doped carbon nano tube and the cobalt nano particle, and the active interface promotes the rearrangement of the electronic structure and transfers more electrons on the metal surface to the carbon layer, thereby optimizing the adsorption energy of hydrogen and improving the kinetics of hydrogen evolution reaction; the extremely small amount of ruthenium nanoclusters in cobalt/carbon nanotubes/ruthenium enhances the corrosion resistance of the catalyst in extreme pH, so that the catalyst has excellent hydrogen evolution performance in the full pH range.
Example 2:
a method for preparing cobalt/carbon nano tube/ruthenium electrocatalyst, comprising the following steps:
(1) Dissolving 150mg of lysozyme into 90mL of aqueous solution to form a clear solution, then dripping the 15mL of aqueous solution of cobalt chloride dissolved with 199.082mg into the solution of lysozyme, uniformly mixing, adding 45mL of aqueous solution dissolved with 9.852g of dimethyl imidazole into the solution, uniformly stirring, standing at room temperature for 24 hours, and collecting a product through centrifugation and freeze drying to obtain dimethyl imidazole cobalt salt/lysozyme;
(2) Heating the obtained dimethyl imidazole cobalt salt/lysozyme to 550 ℃ in nitrogen and preserving heat for 3 hours, and then heating to 900 ℃ and preserving heat for 3 hours to obtain a cobalt/carbon nano tube;
(3) 50mg of the cobalt/carbon nanotube obtained above was weighed and dispersed in 30mL of absolute ethanol, sealed, heated to 60 ℃, stirred at 350rpm for 30min, then added with 5mg of ruthenium chloride trihydrate, kept vigorously stirred at 60 ℃ overnight, then centrifugally dried, heated to 700 ℃ in nitrogen, and kept for 3h to obtain cobalt/carbon nanotube/ruthenium.
The cobalt/carbon nano tube/ruthenium electrocatalyst prepared in the embodiment is applied to the electrolyte to catalyze the hydrogen evolution reaction, and comprises the following steps: the prepared cobalt/carbon nano tube/ruthenium is dispersed in ethanol solution containing perfluorosulfonic polymer, then is loaded on a glassy carbon electrode to serve as a working electrode, a calomel electrode is used as a reference electrode, a carbon rod is used as a counter electrode, proper voltage is applied, and hydrogen evolution is catalyzed in 1.0mol/L potassium hydroxide solution, 0.5mol/L sulfuric acid solution and 1.0mol/L phosphate buffer salt solution which are saturated by argon.
Example 3:
a method for preparing cobalt/carbon nano tube/ruthenium electrocatalyst, comprising the following steps:
(1) Dissolving 300mg of lysozyme into 180mL of aqueous solution to form clear solution, then dripping 30mL of cobalt nitrate hexahydrate aqueous solution dissolved with 892.47mg into the lysozyme solution, uniformly mixing, adding 90mL of aqueous solution dissolved with 19.704g of dimethyl imidazole into the solution, uniformly stirring, standing at room temperature for 24 hours, and collecting a product through centrifugation and freeze drying to obtain dimethyl imidazole cobalt salt/lysozyme;
(2) Heating the obtained dimethyl imidazole cobalt salt/lysozyme to 550 ℃ in nitrogen and preserving heat for 3 hours, and then heating to 900 ℃ and preserving heat for 3 hours to obtain a cobalt/carbon nano tube;
(3) 100mg of the cobalt/carbon nanotube obtained above was weighed and dispersed in 60mL of absolute ethanol, sealed, heated to 60 ℃, stirred at 350rpm for 30min, then 10mg of ruthenium chloride trihydrate was added, vigorously stirred at 60 ℃ overnight, then centrifugally dried, heated to 700 ℃ in nitrogen, and kept at the temperature for 3h to obtain cobalt/carbon nanotube/ruthenium.
The cobalt/carbon nano tube/ruthenium electrocatalyst prepared in the embodiment is applied to the electrolyte to catalyze the hydrogen evolution reaction, and comprises the following steps: the prepared cobalt/carbon nano tube/ruthenium is dispersed in ethanol solution containing perfluorosulfonic polymer, then is loaded on a glassy carbon electrode to serve as a working electrode, a calomel electrode is used as a reference electrode, a carbon rod is used as a counter electrode, proper voltage is applied, and hydrogen evolution is catalyzed in 1.0mol/L potassium hydroxide solution, 0.5mol/L sulfuric acid solution and 1.0mol/L phosphate buffer salt solution which are saturated by argon.
Example 4:
a method for preparing cobalt/carbon nano tube/ruthenium electrocatalyst, comprising the following steps:
(1) Dissolving 100mg of lysozyme into 100mL of aqueous solution to form a clear solution, then dripping 20mL of aqueous solution of cobalt nitrate dissolved with 187.03mg into the lysozyme solution, uniformly mixing, adding 60mL of aqueous solution dissolved with 6.568g of dimethyl imidazole into the solution, uniformly stirring, standing at room temperature for 20h, and collecting a product by centrifugation and freeze drying to obtain dimethyl imidazole cobalt salt/lysozyme;
(2) Heating the obtained dimethyl imidazole cobalt salt/lysozyme to 500 ℃ in nitrogen and preserving heat for 2 hours, and then heating to 850 ℃ and preserving heat for 2 hours to obtain cobalt/carbon nanotubes;
(3) 30mg of the cobalt/carbon nanotube obtained above was weighed and dispersed in 20mL of absolute ethanol, sealed, heated to 50 ℃, stirred for 20min at 300rpm, then 3mg of ruthenium chloride trihydrate was added, and vigorously stirred at 60 ℃ overnight, then centrifugally dried, heated to 650 ℃ in nitrogen, and kept for 2h to obtain cobalt/carbon nanotube/ruthenium.
The cobalt/carbon nano tube/ruthenium electrocatalyst prepared in the embodiment is applied to the electrolyte to catalyze the hydrogen evolution reaction, and comprises the following steps: dispersing the prepared cobalt/carbon nano tube/ruthenium in ethanol solution containing perfluorosulfonic polymer, then loading the ethanol solution on a glassy carbon electrode to serve as a working electrode, taking a calomel electrode as a reference electrode, taking a carbon rod as a counter electrode, applying proper voltage, and catalyzing hydrogen evolution in argon saturated 0.4mol/L potassium hydroxide solution, 0.2mol/L sulfuric acid solution and 0.4mol/L phosphate buffer salt solution.
Example 5:
a method for preparing cobalt/carbon nano tube/ruthenium electrocatalyst, comprising the following steps:
(1) Dissolving 100mg of lysozyme into 50mL of aqueous solution to form a clear solution, then dripping 5mL of aqueous solution of cobalt nitrate dissolved with 187.03mg into the lysozyme solution, uniformly mixing, adding 20mL of aqueous solution dissolved with 6.568g of dimethyl imidazole into the solution, uniformly stirring, standing at room temperature for 30h, and collecting a product by centrifugation and freeze drying to obtain dimethyl imidazole cobalt salt/lysozyme;
(2) Heating the obtained dimethyl imidazole cobalt salt/lysozyme to 600 ℃ in nitrogen and preserving heat for 4 hours, and then heating to 950 ℃ and preserving heat for 4 hours to obtain a cobalt/carbon nano tube;
(3) 30mg of the cobalt/carbon nanotube obtained above was weighed and dispersed in 20mL of absolute ethanol, sealed, heated to 70 ℃, stirred at 400rpm for 40min, then 3mg of ruthenium chloride trihydrate was added, and vigorously stirred at 60 ℃ overnight, then centrifugally dried, heated to 750 ℃ in nitrogen, and kept at the temperature for 4h to obtain cobalt/carbon nanotube/ruthenium.
The cobalt/carbon nano tube/ruthenium electrocatalyst prepared in the embodiment is applied to the electrolyte to catalyze the hydrogen evolution reaction, and comprises the following steps: the prepared cobalt/carbon nano tube/ruthenium is dispersed in ethanol solution containing perfluorosulfonic polymer, then is loaded on a glassy carbon electrode to serve as a working electrode, a calomel electrode is used as a reference electrode, a carbon rod is used as a counter electrode, proper voltage is applied, and hydrogen evolution is catalyzed in 2.0mol/L potassium hydroxide solution, 1.0mol/L sulfuric acid solution and 2.0mol/L phosphate buffer salt solution which are saturated by argon.
According to the invention, lysozyme is used as a matrix, and dimethyl imidazole cobalt salt ZIF-67 grows on the surface of the matrix to obtain a ZIF-67@Lys precursor. And then under the protection of inert atmosphere, ZIF-67@Lys is carbonized at high temperature, cobalt ions are reduced into cobalt particles and the growth of the carbon nano tube is induced, so that the cobalt/carbon nano tube/ruthenium nano cluster composite material electrocatalyst Co@CNT|Ru is prepared in situ. The composite material is not only beneficial to exposing more catalytic active centers, but also combines the unique electron coupling effect of the composite material, so that the Co@CNT|Ru catalyst accelerates the transmission capacity of electrons and protons in the HER process. Co@CNT|Ru electrocatalyst in 1.0M KOH, 0.5. 0.5M H 2 SO 4 Exhibits excellent HER catalytic activity in 1M PBS electrolyte, which reaches 10mA cm -2 The overpotential required for the current density of (a) is only 10mV, 32mV and 63mV respectively, which are all superior to noble metal platinum carbon catalysts.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (9)
1. A method for preparing a cobalt/carbon nano tube/ruthenium electrocatalyst, which is characterized by comprising the following steps:
(1) Adding cobalt salt aqueous solution into lysozyme aqueous solution, uniformly mixing, adding dimethyl imidazole aqueous solution into the mixed solution, uniformly stirring, standing, separating and drying to obtain dimethyl imidazole cobalt salt/lysozyme; the dosage ratio of the cobalt salt to the lysozyme to the dimethylimidazole is (1-3 mmol): (100-300 mg): (0.07-0.2 mol); the concentration of the cobalt salt aqueous solution is 0.05-0.2 mol/L, the concentration of the lysozyme aqueous solution is 1-2 g/L, the concentration of the dimethyl imidazole aqueous solution is 1-3 mol/L, the standing temperature is room temperature, and the standing time is 20-30 h;
(2) Heating and preserving the obtained dimethyl imidazole cobalt salt/lysozyme in inert gas to obtain cobalt/carbon nano tubes; the heating and heat preservation is divided into two sections, wherein the first section is heated at 500-600 ℃, the heat preservation time is 2-4 hours, the second section is heated at 850-950 ℃, and the heat preservation time is 2-4 hours;
(3) Dispersing the obtained cobalt/carbon nano tube in a dispersing agent, sealing, heating and stirring, adding ruthenium salt, stirring overnight, separating and drying, heating and preserving heat in inert gas, and obtaining the cobalt/carbon nano tube/ruthenium electrocatalyst.
2. The method for preparing cobalt/carbon nanotube/ruthenium electrocatalyst according to claim 1, wherein in step (1), the cobalt salt in the aqueous cobalt salt solution is cobalt chloride, cobalt chloride hexahydrate, cobalt nitrate or cobalt nitrate hexahydrate.
3. The method for preparing a cobalt/carbon nanotube/ruthenium electrocatalyst according to claim 1, wherein in step (2), the inert gas is nitrogen.
4. The method for preparing the cobalt/carbon nanotube/ruthenium electrocatalyst according to claim 1, wherein in the step (3), the dispersant is absolute ethanol, the ruthenium salt is ruthenium chloride trihydrate, the dosage ratio of the cobalt/carbon nanotube, the dispersant and the ruthenium salt is (30-100 mg): (20-60 ml): (3-10 mg), the heating temperature is 50-70 ℃ during heating and stirring speed is 300-400 rpm, and the stirring time is 20-40 min.
5. The method for preparing the cobalt/carbon nanotube/ruthenium electrocatalyst according to claim 1, wherein in the step (3), the inert gas is nitrogen, and the heating temperature is 650-750 ℃ and the heat preservation time is 2-4 hours in the heating and heat preservation process.
6. A cobalt/carbon nanotube/ruthenium electrocatalyst prepared by the method according to any one of claims 1 to 5.
7. The use of the cobalt/carbon nanotube/ruthenium electrocatalyst according to claim 6, wherein the electrocatalyst is used in an electrolyte to catalyze hydrogen evolution reactions.
8. The use of a cobalt/carbon nanotube/ruthenium electrocatalyst according to claim 7, wherein the use is specifically: dispersing the electrocatalyst in a dispersing agent, loading the dispersing agent on a substrate electrode to serve as a working electrode, inserting a reference electrode and a counter electrode, applying voltage, and catalyzing hydrogen evolution in an alkaline solution, an acidic solution or a neutral solution saturated by inert gas.
9. The application of the cobalt/carbon nanotube/ruthenium electrocatalyst according to claim 8, wherein the dispersant is an ethanol solution containing a perfluorosulfonic acid polymer, the base electrode is a glassy carbon electrode, the reference electrode is a calomel electrode, the counter electrode is a carbon rod, the inert gas is argon, the alkaline solution is a potassium hydroxide solution, the concentration of the alkaline solution is 0.4 to 2.0mol/L, the acidic solution is a sulfuric acid solution, the concentration of the acidic solution is 0.2 to 1.0mol/L, the neutral solution is a phosphate buffer salt solution, and the concentration of the neutral solution is 0.4 to 2.0mol/L.
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