CN111607763A - Method for rapidly growing metal single atom on carbon-based carrier by microwave-induced metal discharge and application thereof - Google Patents
Method for rapidly growing metal single atom on carbon-based carrier by microwave-induced metal discharge and application thereof Download PDFInfo
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- CN111607763A CN111607763A CN202010553722.5A CN202010553722A CN111607763A CN 111607763 A CN111607763 A CN 111607763A CN 202010553722 A CN202010553722 A CN 202010553722A CN 111607763 A CN111607763 A CN 111607763A
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
Abstract
The invention provides a method for rapidly growing metal single atoms on a carbon-based carrier by microwave-induced metal discharge and application thereof. Firstly, coating a carrier coating containing a carbon-based material on the surface of a discharge bearing container, and then putting a metal wire of a metal monoatomic layer to be grown into the discharge bearing container; placing the discharge bearing container in a microwave generation system, and performing microwave treatment in inert gas such as argon for 10-120 s; in the process, the microwave induces the metal wire to discharge and emit electrons, excites the inert gas medium to generate high-energy plasma, then the high-energy plasma acts on the surface of the metal wire, and induces metal monoatomic atoms to grow and deposit on the surface of the carrier coating after being sputtered from the metal wire; finally, the carrier coating is scraped out, and the carbon-based material loaded with the metal monoatomic is obtained after cleaning and drying. The preparation method provided by the invention is simple and rapid, has low cost, high metal monatomic load and excellent electrocatalysis performance, and is not easy to agglomerate.
Description
Technical Field
The invention belongs to the technical field of functional nano material preparation, and particularly relates to a method for rapidly growing metal single atoms on a carbon-based carrier by microwave-induced metal discharge and application thereof.
Background
The metal monatomic catalyst has only one metal atom per active site which is bonded with adjacent atoms through covalent or ionic interaction, so that the metal sites can be exposed to the maximum extent, and the high efficiency of catalysis is realized. Compared with the micro-nano metal catalyst, the metal monatomic catalyst has the effect of being one to ten and one to hundred, so the metal monatomic catalyst has great research value and application prospect in the fields of energy storage, photo/electro-catalysis and the like. Particularly in the field of electrocatalysis, the metal monatomic catalyst can enable reactants to be adsorbed on the surface of the catalyst to form a stable intermediate, reduce kinetic potential barrier and promote charge transfer in the multi-step oxidation-reduction process.
However, when the size of the metal particles is reduced to a single atom size, the sharply increased surface free energy of the metal particles causes the single atom material to be extremely easy to agglomerate during preparation and application, form nanoclusters and nanoparticles, and possibly cause deactivation of the catalyst and the like. Monatomic catalysts are therefore prone to losing the unique effect of a single atom, which is the greatest challenge in making monatomic materials. At present, the preparation method of metal monoatomic includes mainly a mass separation soft landing method, a high-temperature pyrolysis method, a wet chemical method, an atomic layer deposition method, an electron beam deposition method, a solid-phase melting method, and the like. However, these methods require special equipment, complicated operation or expensive precursors, and have limitations in large-scale application due to high energy consumption and complicated experimental conditions.
For example, patent CN110102300 discloses a flexible carbon-based carrier supported metal monatomic catalyst, and a preparation method and an application thereof, wherein a metal compound, a nitrogen-containing precursor and graphene powder are prepared into mixed slurry, the mixed slurry is coated on a flexible carbon-based carrier, and then multi-step high-temperature pyrolysis treatment is performed in high-purity argon gas to obtain a flexible graphene film supported metal monatomic. The metal single atom is anchored on the carrier through heteroatom coordination, the physical and chemical structure is stable, but the high-temperature pyrolysis process is slow, the preparation time is long, and the control is not easy, so that the method is not suitable for large-scale preparation.
Patent CN108342687 discloses a noble metal monoatomic doped Hf3N4The method comprises the steps of preparing noble metal monoatomic-doped Hf (hafnium) by taking metal Hf/noble metal alloy as a metal target material, ammonia gas and nitrogen gas as nitrogen sources, argon gas as sputtering gas and adopting a magnetron sputtering low-energy deposition technology3N4A film. However, the technology has high requirements on equipment, relatively long sputtering time and high preparation cost.
Therefore, how to simply and efficiently prepare high-quality metal monatomic catalyst is still a challenge.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a method for rapidly growing metal single atoms on a carbon-based carrier by microwave-induced metal discharge and an application thereof. The metal wire is induced to discharge and emit electrons in the argon atmosphere by utilizing microwaves, then the argon is excited to generate plasma, metal atoms are sputtered on the surface of the metal wire in a bombarding mode, the metal atoms move around at high speed and are deposited on a carrier coating on the surface of the discharge bearing container, and therefore the metal single atoms are rapidly grown on the carbon-based carrier.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for rapidly growing metal single atoms on a carbon-based carrier by microwave-induced metal discharge comprises the following steps:
s1, coating a carrier coating containing a carbon-based material on the surface of a discharge bearing container, and then putting a metal wire of a metal monoatomic layer to be grown into the discharge bearing container;
s2, placing the discharge bearing container obtained in the step S1 in a microwave generation system, and carrying out microwave treatment on the discharge bearing container in inert gas to enable metal monoatomic atoms to escape from the metal wire and be loaded on the carrier coating;
s3, scraping the carrier coating obtained in the step S2 out of the discharge bearing container, and then cleaning and drying to obtain the carbon-based material loaded with the metal monoatomic ions.
Further, in step S1, the washcoat further comprises a nitrogen source material.
By adopting the technical scheme, the microwave induces the metal wire to generate dielectric loss, so that free electrons move and vibrate at high speed and are continuously accumulated at the tip. When the electron concentration is high, the tip generates a high-energy electric field to ionize inert gas molecules to form plasma as a conductive medium, and meanwhile, the conductive material on the wall is used as a receiving end to form an electron path to generate electric arcs. The plasma bombards the surface of the metal wire to enable the metal wire to sputter metal atoms, the metal atoms move around at a high speed and are deposited on the conductive carrier coating on the surface of the discharge carrying container, and then the metal atoms and N atoms on the carrier form a bond to form a monoatomic atom; the absorption capacity of the carrier coating layer after the metal monoatomic deposition is enhanced to microwaves, and then the metal monoatomic deposition is induced to be further anchored with the N atom sites of the carbon-based material, so that the metal monoatomic deposition on the carbon-based carrier is realized rapidly and highly.
Further, the nitrogen source material includes but is not limited to one or more of urea, ethylenediamine, glutamic acid, and lysine; the mass of the nitrogen source material is 1-10% of the mass of the carbon-based material.
Preferably, the nitrogen source material is urea. By introducing the nitrogen source material into the carrier coating, under the action of microwave-induced metal wire discharge and generated high-energy plasma, the nitrogen source material in the carrier coating firstly interacts with the carbon-based material to form a nitrogen-doped carbon-based material, so that the content of active sites combined with metal monoatomic atoms in the carrier coating is increased, the metal monoatomic atoms are more easily captured, the growth of the metal monoatomic atoms on the carrier coating is accelerated, and the loading capacity is increased.
Further, the preparation method of the carrier coating comprises the following steps: adding the carbon-based material and the nitrogen source material into an organic solvent, and uniformly dispersing by ultrasonic to obtain a carrier solution; and then coating the carrier solution on the inner wall of the discharge carrying container when the organic solvent in the carrier solution is volatilized until the concentration of the carbon-based material is 10-30mg/mL, so as to obtain the carrier coating. By the method, a layer of conductive carrier coating can be uniformly coated on the inner wall of the discharge bearing container, and the dispersion uniformity of the carbon-based material and the nitrogen source material can be improved, so that the dispersion uniformity of the subsequent metal monoatomic atoms on the surface of the carrier coating is improved.
Further, the carbon-based material includes, but is not limited to, one or more of conductive carbon fiber, conductive carbon black, carbon nanotube, and graphene. The conductive carbon-based material is selected as a carrier, and has the advantages of large specific surface area, good conductivity, easy doping, easy formation of defect sites, interconnected stable structure with metal single atoms and the like. The prepared carbon-based material loaded with metal monoatomic atoms has high activity, high conductivity and excellent volume utilization rate, and can show excellent performance in electrocatalytic hydrogen evolution.
The organic solvent is a volatile organic solvent, including but not limited to one or more of ethanol, propanol, isopropanol, and acetone. The volatile solvent is selected to help accelerate the volatilization of the solvent in the solution, so that a viscous solution with good coating property is formed, and a uniform carrier coating is easily formed on the inner wall of the discharge bearing container.
The metal wire includes but is not limited to one of molybdenum metal wire, tungsten metal wire, copper metal wire, zinc metal wire and nickel metal wire. The preparation method provided by the invention has wider applicability and can be used for rapid deposition and growth of various metal single atoms.
Further, the diameter of the metal wire is 0.1-0.3 cm; the thickness of the washcoat is 0.05-0.3 cm. The loading rate and the loading capacity of metal monoatomic atoms can be regulated and controlled by regulating and controlling the diameter of the metal wire and the thickness of the coating.
Further, the discharge bearing container is a quartz beaker; the microwave generating system is a microwave oven. The method provided by the invention has low requirements on equipment, and can realize rapid deposition and growth of metal monoatomic atoms on the carrier coating by simply using a household microwave oven; and through the growth environment and the position relationship between the carbon-based carrier and the metal wire, sputtered metal atoms can be efficiently diffused and deposited around, and the deposition efficiency is obviously improved.
Further, in step S2, the inert gas is argon. The microwave-induced metal wire discharges energy in an argon atmosphere to generate high-strength plasma as a conductive medium, and meanwhile, the conductive material on the wall is used as a receiving end to form an electronic passage to generate electric arcs. And bombarding the surface of the metal wire by the plasma to sputter metal atoms, wherein the metal atoms move around at a high speed and are deposited on the conductive carrier coating on the surface of the discharge bearing container.
The power of the microwave treatment is 150-900W, such as 150W, 300W, 450W, 600W, 750W, 900W, and the time is 10-120 s. By regulating the microwave power and the microwave treatment time, the growth rate and the loading capacity of the metal monoatomic atoms can be regulated and controlled.
Further, in step S3, the cleaning is performed by using diluted hydrochloric acid and deionized water.
The application of the carbon-based material loaded with metal monoatomic atoms prepared by the method in the fields of energy storage, photo-or electro-catalytic hydrogen evolution and gas adsorption. The metal monoatomic-supported carbon-based material prepared by the invention has high load capacity, high activity and high stability, is used in the fields of energy storage, photo-or electro-catalytic hydrogen evolution, gas adsorption and the like, and shows good performance.
Advantageous effects
Compared with the prior art, the method for rapidly growing the metal monoatomic atom on the carbon-based carrier by microwave-induced metal discharge and the application thereof have the following beneficial effects:
(1) the method for rapidly growing the metal monoatomic atoms on the carbon-based carrier by microwave-induced metal discharge provided by the invention utilizes the microwave to induce the metal wire to generate dielectric loss in the argon atmosphere, so that free electrons move and vibrate at high speed and are continuously accumulated at the tip. When the electron concentration is higher, the tip generates a high-energy electric field to ionize inert gas molecules to generate plasma, metal atoms are sputtered on the surface of the bombarded metal wire, and move around at high speed and are deposited on a carrier coating on the surface of the discharge bearing container, so that the metal single atoms can grow on the carbon-based carrier quickly. Through the technical scheme, the rapid deposition and growth of metal single atoms on the carrier coating can be realized by simply using a household microwave oven; and through the growth environment and the position relationship between the carbon-based carrier and the metal wire, sputtered metal atoms can be efficiently diffused and deposited around, and the deposition efficiency is obviously improved.
(2) The method for rapidly growing the metal monoatomic atom on the carbon-based carrier by microwave-induced metal discharge provided by the invention has the advantages that the nitrogen source material is introduced into the carrier coating, under the action of microwave-induced metal wire discharge and generated high-energy plasma, the nitrogen source material in the carrier coating firstly interacts with the carbon-based material to form the nitrogen-doped carbon-based material, and the content of an active site combined with the metal monoatomic atom in the carrier coating is increased, so that the metal monoatomic atom is more easily captured, the growth of the metal monoatomic atom on the carrier coating is accelerated, and the loading capacity is increased.
(3) The method for rapidly growing the metal monoatomic atoms on the carbon-based carrier by microwave-induced metal discharge provided by the invention has the advantages that the conductive carbon-based material is selected as the carrier, the conductive carbon-based material is coated on the inner wall of a discharge bearing container, and then the metal wire is placed in the container, the raw material types and positions are matched, so that the microwave discharge in the argon atmosphere can be realized, and the deposition and growth of the metal monoatomic atoms sputtered from the metal wire in the carrier coating are promoted. The whole preparation method is simple and quick, has low cost, ensures that the metal monoatomic atoms are not easy to agglomerate, are uniformly dispersed and have high loading capacity, and is suitable for large-scale production.
(4) The metal monoatomic-supported carbon-based carrier prepared by the invention has excellent catalytic performance in electrocatalytic hydrogen evolution, and has great advantages and potentials in the fields of high-performance photo/electrocatalysis, gas adsorption, energy storage and the like.
Drawings
FIGS. 1 a and b are a scanning electron microscope image and a high-resolution transmission electron microscope image, respectively, of conductive carbon Fiber (W-SA/C-Fiber) loaded with a tungsten metal single atom prepared in example 2;
FIG. 2 is a graph showing the electrocatalytic hydrogen evolution performance of 20% Pt/C, C-Fiber and the conductive carbon Fiber loaded with a tungsten metal single atom (W-SA/C-Fiber) prepared in example 2.
FIG. 3 is a high resolution TEM image of the conductive carbon Fiber (Mo-SA/C-Fiber) loaded with Mo metal monoatomic particles prepared in example 3.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1
A method for rapidly growing tungsten metal single atoms on a carbon-based carrier by microwave-induced metal discharge comprises the following steps:
s1, adding 200mg of conductive carbon fiber into 30mL of ethanol solvent, and uniformly mixing for 60s by using 600W power of an ultrasonic cell crusher to obtain a carrier solution; after the ethanol is volatilized until the solution is viscous (the concentration of the conductive carbon fiber is about 20mg/mL), coating the viscous carrier solution on the cup wall of a 200mL quartz beaker by using a brush, wherein the thickness of the carrier coating is about 0.2 cm;
then, a tungsten wire having a length of 5cm and a diameter of 0.2cm was polished with abrasive paper to be bright and placed in the center of the bottom of the quartz beaker.
S2, placing the quartz beaker obtained in the step S1 in a household microwave oven, and continuously introducing argon to perform microwave treatment on the quartz beaker for about 120S, wherein the microwave power is 900W, so that tungsten metal single atoms escape from the tungsten wire and are loaded on the carrier coating.
S3, scraping the carrier coating obtained in the step S2 from the wall of the quartz beaker by using a medicine spoon, then cleaning the carrier coating by using 0.1M dilute hydrochloric acid and deionized water in sequence, and drying the carrier coating to obtain the conductive carbon Fiber (W/C-Fiber) loaded with the tungsten metal monoatomic.
Example 2
A method for rapidly growing tungsten metal single atoms on a carbon-based carrier by microwave-induced metal discharge comprises the following steps:
s1, adding 200mg of conductive carbon fiber and 10mg of urea into 30mL of ethanol solvent, and uniformly mixing for 60s by using 600W power of an ultrasonic cell crusher to obtain a carrier solution; after the ethanol is volatilized until the solution is viscous (the concentration of the conductive carbon fiber is about 20mg/mL), coating the viscous carrier solution on the cup wall of a 200mL quartz beaker by using a brush, wherein the thickness of the carrier coating is about 0.2 cm;
then, a tungsten wire having a length of 5cm and a diameter of 0.2cm was polished with abrasive paper to be bright and placed in the center of the bottom of the quartz beaker.
S2, placing the quartz beaker obtained in the step S1 in a household microwave oven, and continuously introducing argon to perform microwave treatment on the quartz beaker for about 120S, wherein the microwave power is 900W, so that tungsten metal single atoms escape from the tungsten wire and are loaded on the carrier coating; the rapid deposition and growth of metal monoatomic atoms on the carrier coating can be realized only by simply using a household microwave oven; and through the growth environment and the position relationship between the carbon-based carrier and the metal wire, sputtered metal atoms can be efficiently diffused and deposited around, and the deposition efficiency is obviously improved.
S3, scraping the carrier coating obtained in the step S2 from the wall of the quartz beaker by using a medicine spoon, then cleaning the carrier coating by using 0.1M dilute hydrochloric acid and deionized water in sequence, and drying the carrier coating to obtain the conductive carbon Fiber (W-SA/C-Fiber) loaded with the tungsten metal monoatomic.
Referring to fig. 1, it can be seen that, by using the preparation method provided by the present invention, tungsten metal monoatomic atoms are successfully grown on the surface of the conductive carbon fiber, and the distribution uniformity of the tungsten metal monoatomic atoms is good.
The electro-catalytic hydrogen evolution performance of the conductive carbon Fiber, the 20 wt% Pt/C material and the conductive carbon Fiber (W-SA/C-Fiber) loaded with tungsten metal monoatomic material prepared in this example were respectively tested, and the test results are shown in FIG. 2. It can be seen that the starting peak potential is small, the Tafel value is 55mV/dec, and the electrocatalytic hydrogen evolution performance is excellent.
Example 3
A method for rapidly growing molybdenum metal single atoms on a carbon-based carrier by microwave-induced metal discharge comprises the following steps:
s1, adding 200mg of conductive carbon fiber and 10mg of urea into 30mL of ethanol solvent, and uniformly mixing for 60s by using 600W power of an ultrasonic cell crusher to obtain a carrier solution; after the ethanol is volatilized until the solution is viscous (the concentration of the conductive carbon fiber is about 25mg/mL), coating the viscous carrier solution on the cup wall of a 200mL quartz beaker by using a brush, wherein the thickness of the carrier coating is about 0.1 cm;
polishing and brightening a molybdenum metal wire with the length of 5cm and the diameter of 0.2cm by using abrasive paper, and placing the molybdenum metal wire into the center of the bottom of the quartz beaker;
s2, placing the quartz beaker obtained in the step S1 in a household microwave oven, and continuously introducing argon to perform microwave treatment on the quartz beaker for about 100S, wherein the microwave power is 900W, so that molybdenum metal single atoms escape from the molybdenum metal wires and are loaded on the carrier coating;
s3, scraping the carrier coating obtained in the step S2 from the wall of the quartz beaker by using a medicine spoon, then cleaning the carrier coating by using 0.1M dilute hydrochloric acid and deionized water in sequence, and drying the carrier coating to obtain the conductive carbon Fiber (Mo-SA/C-Fiber) loaded with the molybdenum metal monoatomic.
As shown in fig. 3, it can be seen that the molybdenum metal monoatomic atoms are successfully grown on the surface of the conductive carbon fiber in the embodiment, and the distribution uniformity of the molybdenum metal monoatomic atoms is good.
Example 4
A method for rapidly growing copper metal monoatomic atoms on a carbon-based carrier by microwave-induced metal discharge comprises the following steps:
s1, adding 200mg of conductive carbon fiber and 10mg of urea into 30mL of ethanol solvent, and uniformly mixing for 60s by using 600W power of an ultrasonic cell crusher to obtain a carrier solution; after the ethanol is volatilized until the solution is viscous (the concentration of the conductive carbon fiber is about 15mg/mL), coating the viscous carrier solution on the cup wall of a 200mL quartz beaker by using a brush, wherein the thickness of the carrier coating is about 0.1 cm;
polishing and brightening a copper metal wire with the length of 5cm and the diameter of 0.2cm by using abrasive paper, and placing the copper metal wire into the center of the bottom of the quartz beaker;
s2, placing the quartz beaker obtained in the step S1 in a household microwave oven, and continuously introducing argon to perform microwave treatment on the quartz beaker for about 100S, wherein the microwave power is 750W, so that copper metal monoatomic atoms escape from the copper metal wire and are loaded on the carrier coating;
s3, scraping the carrier coating obtained in the step S2 from the wall of the quartz beaker by using a medicine spoon, then cleaning the carrier coating by using 0.1M dilute hydrochloric acid and deionized water in sequence, and drying the carrier coating to obtain the conductive carbon Fiber (Cu-SA/C-Fiber) loaded with copper metal monoatomic atoms.
Example 5
A method for rapidly growing zinc metal single atoms on a carbon-based carrier by microwave-induced metal discharge comprises the following steps:
s1, adding 100mg of conductive carbon fiber and 10mg of urea into 20mL of ethanol solvent, and uniformly mixing for 60s by using 600W power of an ultrasonic cell crusher to obtain a carrier solution; after the ethanol is volatilized until the solution is viscous (the concentration of the conductive carbon fiber is about 15mg/mL), coating the viscous carrier solution on the cup wall of a 200mL quartz beaker by using a brush, wherein the thickness of the carrier coating is about 0.2 cm;
polishing zinc wire with length of 5cm and diameter of 0.2cm with sand paper, and placing into the center of the bottom of the quartz beaker;
s2, placing the quartz beaker obtained in the step S1 in a household microwave oven, and continuously introducing argon to perform microwave treatment on the quartz beaker for about 60S, wherein the microwave power is 750W, so that zinc metal monoatomic atoms escape from the zinc metal wires and are loaded on the carrier coating;
s3, scraping the carrier coating obtained in the step S2 from the wall of the quartz beaker by using a medicine spoon, then cleaning the carrier coating by using 0.1M dilute hydrochloric acid and deionized water in sequence, and drying the carrier coating to obtain the conductive carbon Fiber (Zn-SA/C-Fiber) loaded with the zinc metal monoatomic.
Example 6
A method for rapidly growing nickel metal single atoms on a carbon-based carrier by microwave-induced metal discharge comprises the following steps:
s1, adding 100mg of conductive carbon fiber and 8mg of urea into 30mL of ethanol solvent, and uniformly mixing for 60s by using 600W power of an ultrasonic cell crusher to obtain a carrier solution; after the ethanol is volatilized until the solution is viscous (the concentration of the conductive carbon fiber is about 30mg/mL), coating the viscous carrier solution on the cup wall of a 200mL quartz beaker by using a brush, wherein the thickness of the carrier coating is about 0.2 cm;
polishing nickel metal wires with the length of 5cm and the diameter of 0.2cm by using abrasive paper to be bright, and placing the nickel metal wires in the center of the bottom of the quartz beaker;
s2, placing the quartz beaker obtained in the step S1 in a household microwave oven, and continuously introducing argon to perform microwave treatment on the quartz beaker for about 80S, wherein the microwave power is 750W, so that nickel metal single atoms escape from the nickel metal wires and are loaded on the carrier coating;
s3, scraping the carrier coating obtained in the step S2 from the wall of the quartz beaker by using a medicine spoon, then cleaning the carrier coating by using 0.1M dilute hydrochloric acid and deionized water in sequence, and drying the carrier coating to obtain the conductive carbon Fiber (Ni-SA/C-Fiber) loaded with the nickel metal monoatomic.
In summary, the present invention utilizes microwave to induce metal wire in argon atmosphere to generate dielectric loss, which results in high speed movement and vibration of free electrons and continuous accumulation at the tip. When the electron concentration is higher, the tip generates a high-energy electric field to ionize inert gas molecules to generate plasma, metal atoms are sputtered on the surface of the bombarded metal wire, and move around at high speed and are deposited on a carrier coating on the surface of the discharge bearing container, so that the metal single atoms can grow on the carbon-based carrier quickly. Through the technical scheme, the rapid deposition and growth of metal single atoms on the carrier coating can be realized by simply using a household microwave oven; and through the growth environment and the position relationship between the carbon-based carrier and the metal wire, sputtered metal atoms can be efficiently diffused and deposited around, and the deposition efficiency is obviously improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for rapidly growing metal single atoms on a carbon-based carrier by microwave-induced metal discharge is characterized by comprising the following steps:
s1, coating a carrier coating containing a carbon-based material on the surface of a discharge bearing container, and then putting a metal wire of a metal monoatomic layer to be grown into the discharge bearing container;
s2, placing the discharge bearing container obtained in the step S1 in a microwave generation system, and carrying out microwave treatment on the discharge bearing container in inert gas to enable metal monoatomic atoms to escape from the metal wire and be loaded on the carrier coating;
s3, scraping the carrier coating obtained in the step S2 out of the discharge bearing container, and then cleaning and drying to obtain the carbon-based material loaded with the metal monoatomic ions.
2. The method of claim 1, wherein the washcoat further comprises a nitrogen source material in step S1.
3. The method of claim 2, wherein the nitrogen source material includes but is not limited to one or more of urea, ethylenediamine, glutamic acid, lysine; the mass of the nitrogen source material is 1-10% of the mass of the carbon-based material.
4. A method for rapid growth of metal single atoms on a carbon based support by microwave induced metal discharge according to any of claims 1 to 3, wherein the washcoat is prepared by a method comprising: adding the carbon-based material and the nitrogen source material into an organic solvent, and uniformly dispersing by ultrasonic to obtain a carrier solution; and then coating the carrier solution on the inner wall of the discharge carrying container when the organic solvent in the carrier solution is volatilized until the concentration of the carbon-based material is 10-30mg/mL, so as to obtain the carrier coating.
5. The method of claim 4, wherein the carbon-based material includes but is not limited to one or more of conductive carbon fiber, conductive carbon black, carbon nanotube, graphene; the organic solvent is a volatile organic solvent, and includes but is not limited to one or more of ethanol, propanol, isopropanol and acetone; the metal wire includes but is not limited to one of molybdenum metal wire, tungsten metal wire, copper metal wire, zinc metal wire and nickel metal wire.
6. A method for the rapid growth of metal monoatomic ions on carbon-based supports by microwave induced metal discharge according to claim 1 or 4, wherein the diameter of the metal wire is 0.1-0.3 cm; the thickness of the washcoat is 0.05-0.3 cm.
7. The method of claim 1, wherein the discharge-carrying vessel is a quartz beaker; the microwave generating system is a microwave oven.
8. The method for rapid growth of metal monoatomic ions on a carbon-based carrier by microwave induced metal discharge according to claim 1, wherein in the step S2, the inert gas is argon; the power of the microwave treatment is 150-900W, and the time is 10-120 s.
9. The method for rapidly growing metal monoatomic ions on a carbon-based carrier through microwave-induced metal discharge according to claim 1, wherein the cleaning is performed with diluted hydrochloric acid and deionized water in step S3.
10. Use of a metal-monatomic-loaded carbon-based material prepared by the method according to any one of claims 1 to 9, characterized in that it is used in the fields of energy storage, photo-or electrocatalytic hydrogen evolution and gas sorption.
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