CN108385124B - Preparation method of transition metal/carbon tube/graphene electrocatalyst for hydrogen evolution reaction - Google Patents
Preparation method of transition metal/carbon tube/graphene electrocatalyst for hydrogen evolution reaction Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 20
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 20
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000001257 hydrogen Substances 0.000 title claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 66
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000010457 zeolite Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 43
- 239000011259 mixed solution Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 5
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 5
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 5
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229940075397 calomel Drugs 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 230000001808 coupling effect Effects 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 Platinum group metals Chemical class 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
The invention discloses a preparation method of a transition metal/carbon tube/graphene electrocatalyst for hydrogen evolution reaction. The preparation method comprises the steps of taking a core-shell bimetallic zeolite imidazolyl framework coated by graphene oxide as a precursor, thermally reducing GO into rGO by a one-step heating method, and simultaneously carbonizing ZIF-67@ ZIF-8 nano particles in situ into N-doped carbon nano tubes coated with superfine Co nano particles to prepare the Co @ N-CNTs @ rGO composite material. Due to the advantages of unique three-dimensional hierarchical structure, high porosity, rich N doping, high conductivity of rGO, uniform dispersion of Co nanoparticles and the like, the composite material shows excellent electrocatalytic properties when used as a catalyst for HER. The composite material obtained by the invention has the advantages of strong conductivity, many active sites, good electrocatalytic performance, low cost of raw materials for preparation, simple process, low reaction energy consumption, realization of large-scale preparation, and high efficiency and economy.
Description
Technical Field
The invention belongs to the technical field of materials and energy, and particularly relates to a transition metal/carbon nanotube/graphene three-dimensional hierarchical composite electrocatalyst for efficient hydrogen evolution reaction and a preparation method thereof.
Background
With the increasing severity of environmental issues and the emergence of energy shortage, the development of green and sustainable energy conversion and storage technologies has become the center of research of many researchers at present. Hydrogen has high calorific value and is environmentally friendly, which is a focus of scientific attention. The electrolysis of hydrogen to produce hydrogen is of particular interest because of its high efficiency, convenience and environmental protection. However, the electrolytic water cathode reaction involves a multi-step proton-coupled electron transfer process, which is slow in reaction thermodynamics and kinetics, resulting in a need for a high overpotential in the electrolytic water Hydrogen Evolution Reaction (HER). Therefore, in order to solve this problem, it is urgently required to develop a novel electrocatalyst for decreasing the reaction energy barrier and increasing the reaction rate. Platinum group metals are currently the most effective of HER electrocatalysts, but their widespread use in commercial electrolytes is severely hampered by the high cost of Pt due to its limited reserves in nature.
Therefore, in recent years researchers have also conducted a great deal of research in order to find alternative methods to noble metal HER catalysts, such as 3d transition group metals (Fe, Co, Ni) and their corresponding compounds such as sulfides, phosphides, etc. Among these, hybrid composites of a particular transition group metal with a nitrogen-doped carbon matrix have attracted considerable attention in HER due to their unique structure and composition, relatively low metal consumption. Nevertheless, these hybrid composite materials also face problems, such as tedious preparation process, high cost, large metal particle size, poor dispersibility, easy agglomeration, etc., which results in reduction of catalytic activity and stability, and thus there is a need to develop a novel economic and efficient HER electrocatalyst for electrolysis of water.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a transition metal/carbon tube/graphene three-dimensional hierarchical composite electrocatalyst with high efficiency, low cost, high catalytic activity and good stability.
The invention provides a transition metal/carbon tube/graphene three-dimensional grading composite material electrocatalyst, which is prepared from the following raw materials in parts by weight: graphene oxide, zinc salt, cobalt salt, Cetyl Trimethyl Ammonium Bromide (CTAB), and dimethyl imidazole.
The invention provides a transition metal/carbon tube/graphene three-dimensional hierarchical composite material electrocatalyst for high-efficiency HER, which comprises the following preparation processes: the preparation method comprises the steps of using a graphene-wrapped core-shell bimetallic organic framework (ZIF-67 @ ZIF-8@ GO) as a template, carrying out thermal reduction of the GO and carbonization of the ZIF-67@ ZIF-8 at the same time at high temperature under the protection of inert atmosphere, and preparing a transition metal/carbon nano tube/graphene composite material electrocatalyst Co @ N-CNTs @ rGO in situ. The prepared composite material has a unique three-dimensional hierarchical structure and a high specific surface area, effectively inhibits the agglomeration of transition metal Co nanoparticles, and fully exposes the active sites of cobalt; secondly, the composite material is beneficial to the transmission of electrons due to the excellent conductivity of the composite materialThe overall conductivity of the composite material is improved; the material has rich N doping, can realize better synergistic effect, and shows excellent electrocatalytic properties (respectively 108 mV (1M KOH) and 86 mV (0.5M H)2SO4) RHE to a current density of 10 milliamps per square centimeter).
The preparation method of the transition metal/carbon nanotube/graphene three-dimensional graded composite material electrocatalyst (Co @ N-CNTs @ rGO) for the efficient hydrogen evolution reaction comprises the following specific steps:
(1) a cubic ZIF-8 template (ZIF-8 @ GO) of composite graphene is prepared by coprecipitation method, wherein 150 ~ 300 mg of Zn (NO) is added3)2·6H2Adding the mixed solution into 40 mL of 2-methylimidazole solution, stirring at room temperature for 30min, centrifugally separating a product, cleaning for 3-4 times by using an ethanol solution, finally placing the product in a freeze dryer at the temperature of-50 ℃, and freeze-drying for 36 3572 h to obtain a product, namely ZIF-8@ GO;
(2) preparing a graphene-coated core-shell bimetallic zeolite imidazolyl framework (ZIF-67 @ ZIF-8@ GO), weighing 100 mg of ZIF-8@ GO obtained in the step (1), uniformly dispersing the ZIF-8@ GO in a methanol solution, carrying out ultrasonic treatment for 20 min, adding a certain amount of 3mL of 2-methylimidazole solution into the obtained solution, stirring for 10 min to obtain a mixed solution, transferring the mixed solution into a 100mL high-pressure reaction kettle, placing the mixed solution into a constant temperature box with the temperature of 90 ~ ℃, reacting for 12 h, cooling at room temperature, carrying out centrifugal separation on a product, washing the product for 3-4 times by using the methanol solution, finally placing the product into a freeze dryer with the temperature of-50 ℃, and carrying out freeze drying for 36 ~ h to obtain the ZIF-67@ ZIF-8 GO, wherein the methanol solution contains 3 mg of CTAB and a certain amount of CoCl2·6H2O；
(3) Preparing a three-dimensional grading composite material (Co @ N-CNTs @ rGO) of transition metal/carbon nano tube/graphene, namely taking ZIF-67@ ZIF-8@ GO prepared in the step (2) as a precursor, weighing a proper amount of the precursor, placing the precursor into a porcelain boat, placing the porcelain boat into a tubular furnace, introducing argon, heating to 800 ~ 1000 ℃ at the speed of 2 ℃/min, and preserving heat for 6 hours at the temperature to obtain the Co @ N-CNTs @ rGO composite material.
The Co @ N-CNTs @ rGO composite material prepared by the invention can be used for catalyzing hydrogen evolution reaction, and comprises the following specific steps: the prepared Co @ N-CNTs @ rGO composite material is loaded on a glassy carbon electrode to serve as a working electrode, a calomel electrode serves as a reference electrode, and a carbon rod serves as a counter electrode. The electrochemical performance was tested in a 1.0M KOH solution saturated with argon and a 0.5M sulfuric acid solution.
The invention has the advantages that: (1) in the prepared Co @ N-CNTs @ rGO composite material, the size of the transition metal nano particles is very small (less than 10 nanometers), and a strong interface coupling effect is formed between the transition metal nano particles and the N-CNTs; (2) the Co @ N-CNTs @ rGO composite material has a unique three-dimensional hierarchical structure and a large specific surface area, so that the application of the Co @ N-CNTs @ rGO composite material in the aspect of electrocatalysis can keep high catalytic activity and excellent stability; (3) the preparation raw materials only relate to common reagents such as zinc nitrate hexahydrate, cobalt chloride hexahydrate, dimethyl imidazole, graphene, CTAB, methanol and ethanol, the cost is low, the product purity is high, the preparation process is simple, the industrial production is easy to realize, and the preparation process can be further expanded to the preparation of other transition metal/carbon nanotube/graphene three-dimensional hierarchical composite electrocatalysts.
The invention provides a preparation method and application of a Co @ N-CNTs @ rGO composite material, which is efficient, low in cost, good in stability and easy for industrial production.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the Co @ N-CNTs @ rGO composite prepared in example 1 of the present invention. Wherein: (a) the low power scanning electron microscope image and (b) the high power scanning electron microscope image.
FIG. 2 is a Transmission Electron Microscope (TEM) image of the Co @ N-CNTs @ rGO composite prepared in example 1 of the present invention. Wherein: (a) the image is a low-power transmission electron microscope image, (b) a high-resolution transmission electron microscope image, and (c) a local enlarged image.
FIG. 3 is an energy spectrum elemental analysis (EDS) plot of the Co @ N-CNTs @ rGO composite prepared in example 1 of the present invention.
FIG. 4 is an X-ray diffraction energy spectrum (XRD) analysis of the Co @ N-CNTs @ rGO composite prepared in example 1 of the present invention.
FIG. 5 is a linear sweep voltammogram of the Co @ N-CNTs @ rGO composite prepared in example 1 of the present invention at a sweep rate of 5 millivolts per second in 1.0 mole per liter of KOH electrolyte.
FIG. 6 is a linear sweep voltammogram of the Co @ N-CNTs @ rGO composite prepared in example 1 of the present invention at a sweep rate of 5 millivolts per second in a sulfuric acid electrolyte of 0.5 moles per liter.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples. For a further understanding of the invention, reference is made to the following examples and accompanying drawings.
Example 1, a Co @ N-CNTs @ rGO composite material, a method for preparing the same and applications thereof, comprising the steps of:
(1) a cubic ZIF-8 template (ZIF-8 @ GO) of composite graphene is prepared by coprecipitation method, wherein 150 ~ 300 mg of Zn (NO) is added3)2·6H2Adding the mixed solution into 40 mL of 2-methylimidazole solution, stirring at room temperature for 30min, centrifugally separating a product, cleaning for 3-4 times by using an ethanol solution, finally placing the product in a freeze dryer at the temperature of-50 ℃, and freeze-drying for 36 3572 h to obtain a product, namely ZIF-8@ GO;
(2) preparation of core-shell bimetallic zeolite imidazolyl framework wrapped by graphene (ZIF-67 @ ZIF-8@ GO), weighing 100 mg of ZIF-8@ GO obtained in the step (1), uniformly dispersing in a methanol solution, performing ultrasonic treatment for 20 min, adding 3mL of 2-methylimidazole solution into the obtained solution, stirring for 10 min to obtain a mixed solution, transferring the mixed solution into a 100mL high-pressure reaction kettle, placing the mixed solution into a constant temperature box with the temperature of 90 ~ ℃, reacting for 12 h, cooling at room temperature, centrifugally separating the product, washing the product for 3-4 times by using the methanol solution, finally placing the product into a freeze dryer with the temperature of-50 ℃, freeze-drying for 36 ~ h,the obtained product is ZIF-67@ ZIF-8@ GO; wherein: the methanol solution contained 3 mg CTAB and a certain amount of CoCl2·6H2O；
(3) Preparation of transition metal/carbon nanotube/graphene three-dimensional hierarchical composite (Co @ N-CNTs @ rGO): taking the ZIF-67@ ZIF-8@ GO prepared in the step (2) as a precursor, weighing a proper amount of the precursor, placing the precursor into a porcelain boat, placing the porcelain boat into a tube furnace, introducing argon, heating to 900 ℃ at the speed of 2 ℃/min, and preserving heat for 6h at the temperature to obtain the Co @ N-CNTs @ rGO composite material.
The Co @ N-CNTs @ rGO composite material prepared by the invention can be used for catalyzing hydrogen evolution reaction, and comprises the following specific steps: the prepared composite material is loaded on a glassy carbon electrode to serve as a working electrode, a calomel electrode serves as a reference electrode, and a carbon rod serves as a counter electrode. The electrochemical performance was tested in a 1.0M KOH solution saturated with argon and a 0.5M sulfuric acid solution.
The beneficial effect of this embodiment does: (1) in the prepared Co @ N-CNTs @ rGO composite material, the size of cobalt nanoparticles is very small (less than 10 nm), and a strong interface coupling effect is formed between the cobalt nanoparticles and the N-CNTs; (2) the Co @ N-CNTs @ rGO composite material has a unique three-dimensional hierarchical structure and a large specific surface area, so that the application of the Co @ N-CNTs @ rGO composite material in the aspect of electrocatalysis can keep high catalytic activity and excellent stability; (3) the preparation raw materials only relate to common reagents such as zinc nitrate hexahydrate, cobalt chloride hexahydrate, dimethyl imidazole, graphene, CTAB, methanol and ethanol, the cost is low, the product purity is high, the preparation process is simple, the industrial production is easy to realize, and the preparation process can be further expanded to the preparation of other transition metal/carbon nanotube/graphene three-dimensional hierarchical composite electrocatalysts.
(1) a cubic ZIF-8 template (ZIF-8 @ GO) of composite graphene is prepared by coprecipitation method, wherein 300 ~ 400 mg of Zn (NO) is added3)2·6H2Adding O and 5 mg of CTAB into 10 mL of graphene oxide turbid liquid respectively, and fully stirring to obtain a mixed solution; adding the mixture to 4Stirring for 30min at room temperature in 0mL of 2-methylimidazole solution, performing centrifugal separation on the product, washing for 3-4 times by using an ethanol solution, and finally placing the product in a freeze dryer at the temperature of-50 ℃ for freeze drying for 36 ~ 72 h to obtain a product, namely ZIF-8@ GO;
(2) preparing a graphene-coated core-shell bimetallic zeolite imidazolyl framework (ZIF-67 @ ZIF-8@ GO), weighing 100 mg of ZIF-8@ GO obtained in the step (1), uniformly dispersing the ZIF-8@ GO in 23 mL of methanol solution, carrying out ultrasonic treatment for 20 min, adding 3mL of 895 mg of 2-methylimidazole solution into the obtained solution, stirring for 10 min to obtain a mixed solution, transferring the mixed solution into a 100mL high-pressure reaction kettle, placing the mixed solution into a constant temperature box with the temperature of 90 ~ 100 ℃, reacting for 12 h, cooling at room temperature, carrying out centrifugal separation on a product, washing for 3-4 times by using the methanol solution, finally placing the product into a freeze dryer with the temperature of-50 ℃, and carrying out freeze drying for 48 h to obtain the ZIF-67F-8 @ GO, wherein the methanol solution contains 3 mg of CTAB and a certain amount of CoCl @ GO2·6H2O；
(3) Preparation of transition metal/carbon nanotube/graphene three-dimensional hierarchical composite (Co @ N-CNTs @ rGO): taking the ZIF-67@ ZIF-8@ GO prepared in the step (2) as a precursor, weighing a proper amount of the precursor, placing the precursor into a porcelain boat, placing the porcelain boat into a tube furnace, introducing argon, heating to 900 ℃ at the speed of 2 ℃/min, and preserving heat for 6h at the temperature to obtain the Co @ N-CNTs @ rGO composite material.
The Co @ N-CNTs @ rGO composite material prepared by the invention can be used for catalyzing hydrogen evolution reaction, and comprises the following specific steps: the prepared composite material is loaded on a glassy carbon electrode to serve as a working electrode, a calomel electrode serves as a reference electrode, and a carbon rod serves as a counter electrode. The electrochemical performance was tested in a 1.0M KOH solution saturated with argon and a 0.5M sulfuric acid solution.
The beneficial effect of this embodiment does: (1) in the prepared Co @ N-CNTs @ rGO composite material, the size of cobalt nanoparticles is very small (less than or equal to 10 nm), and a strong interface coupling effect is formed between the cobalt nanoparticles and the N-CNTs; (2) the Co @ N-CNTs @ rGO composite material has a unique three-dimensional hierarchical structure and a large specific surface area, so that the application of the Co @ N-CNTs @ rGO composite material in the aspect of electrocatalysis can keep high catalytic activity and excellent stability; (3) the preparation raw materials only relate to common reagents such as zinc nitrate hexahydrate, cobalt chloride hexahydrate, dimethyl imidazole, graphene, CTAB, methanol and ethanol, the cost is low, the product purity is high, the preparation process is simple, the industrial production is easy to realize, and the preparation process can be further expanded to the preparation of other transition metal/carbon nanotube/graphene three-dimensional hierarchical composite electrocatalysts.
Example 3, a Co @ N-CNTs @ rGO composite material, a method for preparing the same and applications thereof, comprising the steps of:
(1) preparing a cubic ZIF-8 template (ZIF-8 @ GO) of the composite graphene by adopting a coprecipitation method: 82.5 mg of Zn (NO)3)2·6H2Adding O and 5 mg of CTAB into 10 mL of graphene oxide turbid liquid respectively, and fully stirring to obtain a mixed solution; adding the mixed solution into 40 mL of 2.825 g of 2-methylimidazole solution, stirring at room temperature for 30min, centrifugally separating the product, washing with an ethanol solution for 3-4 times, and finally placing in a freeze dryer at-50 ℃ for freeze drying for 72 h to obtain a product, namely ZIF-8@ GO;
(2) preparation of graphene-coated core-shell bimetallic zeolite imidazolyl framework (ZIF-67 @ ZIF-8@ GO), namely weighing 50mg of ZIF-8@ GO obtained in the step (1), uniformly dispersing the ZIF-8@ GO in 23 mL of methanol solution, carrying out ultrasonic treatment for 20 min, adding 3mL of a certain amount of 2-methylimidazole solution into the obtained solution, stirring for 10 min to obtain a mixed solution, transferring the mixed solution into a 100mL high-pressure reaction kettle, placing the mixed solution into a constant temperature box of 90 ~ 100 ℃, reacting for 12 h, cooling at room temperature, carrying out centrifugal separation on a product, washing for 3-4 times by using the methanol solution, finally placing the product into a freeze dryer of-50 ℃, and carrying out freeze drying for 48 h to obtain the ZIF-67@ ZIF-8 GO, wherein the methanol solution contains 3 mg of CTAB and a certain amount of CoCl2·6H2O and NiCl2·6H2O；
(3) Preparing a three-dimensional grading composite material (Co @ N-CNTs @ rGO) of transition metal/carbon nano tube/graphene, namely taking ZIF-67@ ZIF-8@ GO prepared in the step (2) as a precursor, weighing a proper amount of the precursor, placing the precursor into a porcelain boat, placing the porcelain boat into a tubular furnace, introducing argon, heating to 800 ~ 1000 ℃ at the speed of 2 ℃/min, and preserving heat for 6 hours at the temperature to obtain the Co @ N-CNTs @ rGO composite material.
The Co @ N-CNTs @ rGO composite material prepared by the invention can be used for catalyzing hydrogen evolution reaction, and comprises the following specific steps: the prepared composite material is loaded on a glassy carbon electrode to serve as a working electrode, a calomel electrode serves as a reference electrode, and a carbon rod serves as a counter electrode. The electrochemical performance was tested in a 1.0M KOH solution saturated with argon and a 0.5M sulfuric acid solution.
The beneficial effect of this embodiment does: (1) in the prepared Co @ N-CNTs @ rGO composite material, the size of cobalt nanoparticles is very small (less than 10 nm), and a strong interface coupling effect is formed between the cobalt nanoparticles and the N-CNTs; (2) the Co @ N-CNTs @ rGO composite material has a unique three-dimensional hierarchical structure and a large specific surface area, so that the application of the Co @ N-CNTs @ rGO composite material in the aspect of electrocatalysis can keep high catalytic activity and excellent stability; (3) the preparation raw materials only relate to common reagents such as zinc nitrate hexahydrate, cobalt chloride hexahydrate, dimethyl imidazole, graphene, CTAB, methanol and ethanol, the cost is low, the product purity is high, the preparation process is simple, the industrial production is easy to realize, and the preparation process can be further expanded to the preparation of other transition metal/carbon nanotube/graphene three-dimensional hierarchical composite electrocatalysts.
Claims (3)
1. A preparation method of a transition metal/carbon tube/graphene electrocatalyst for hydrogen evolution reaction is characterized by comprising the following specific steps:
(1) preparing a cubic ZIF-8 template ZIF-8@ GO of composite graphene by adopting a coprecipitation method, namely preparing 150 ~ 300 mg of Zn (NO)3)2·6H2Adding the mixed solution into 50 ~ mL of 2-methylimidazole solution, stirring at room temperature for 30min, performing centrifugal separation on a product, cleaning the product for 3-4 times by using ethanol solution, and finally placing the product in a freeze dryer at the temperature of-50 ℃ for freeze drying for 36 3572 h to obtain a product, namely ZIF-8@ GO;
(2) preparation of core-shell bimetallic zeolite imidazolyl framework wrapped by graphene ZIF-67@ ZIF-8@ GO, weighing 100 ~ mg of ZIF-8@ GO obtained in the step (1), uniformly dispersing the ZIF-8@ GO in 10 ~ mL of methanol solution, carrying out ultrasonic treatment for 20 min, adding 2 ~ mL of 2-methylimidazole solution into the obtained solution, stirring for 10 min to obtain mixed solution, transferring the mixed solution into a 100mL high-pressure reaction kettle, placing the high-pressure reaction kettle in a thermostat at 80 ~ ℃ for 10 ~ h, cooling at room temperature, carrying out centrifugal separation on the product, washing with the methanol solution for 3-4 times, finally placing the product in a freeze dryer at-50 ℃ for freeze drying for 36 ~ 72 h to obtain the ZIF-67@ ZIF-8@ GO, wherein the methanol solution contains 2 ~ mg of CTAB and 150 ~ mg of CoCl2·6H2O；
(3) Preparing Co @ N-CNTs @ rGO from a transition metal/carbon nano tube/graphene three-dimensional grading composite material, namely taking ZIF-67@ ZIF-8@ GO prepared in the step (2) as a precursor, weighing a proper amount of the precursor, placing the precursor into a ceramic boat, placing the ceramic boat into a tubular furnace, introducing argon, heating to 800 ~ 1000 ℃ at the speed of 2 ℃/min, and preserving heat at the temperature for 6 hours to obtain the Co @ N-CNTs @ rGO composite material.
2. A Co @ N-CNTs @ rGO composite obtained by the preparation process of claim 1.
3. The application of the Co @ N-CNTs @ rGO composite material prepared by the preparation method of claim 1 in a hydrogen evolution reaction catalyst.
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