CN111072018A - Preparation method and application of metal-loaded nitrogen-doped folded graphene - Google Patents
Preparation method and application of metal-loaded nitrogen-doped folded graphene Download PDFInfo
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/34—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The invention discloses a preparation method and application of metal-loaded nitrogen-doped folded graphene, which are characterized in that graphene oxide, ethylenediamine-terminated polyvinylamine and corresponding metal salt are used as raw materials, the graphene oxide is firstly dispersed into a certain solvent to form a solution A, a certain amount of ethylenediamine-terminated polyvinylamine solution with a certain concentration is prepared, a certain amount of metal salt is added into the solution to form a solution B, then A, B two solutions are mixed and stirred, hydrothermal reaction is carried out in a hydrothermal reaction kettle, after cooling, solids are collected, and the final product can be prepared by washing and drying. The experimental process is simple, the operability is strong, and the industrial popularization is facilitated; the prepared metal-loaded nitrogen-doped folded graphene has the advantages of large specific surface area, a large number of folds, rich pores, good structure retentivity, uniform nitrogen element doping and uniform loaded metal, greatly changes the catalytic and electrochemical properties of the graphene, and widens the application of the graphene in the fields of catalysis and energy storage.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method and application of metal-loaded nitrogen-doped folded graphene.
Background
Since the carbon material exists in various forms and is the most widely used material in the world, graphene, which is one of the carbon materials, is considered as an ideal carrier of a monoatomic dispersion catalyst due to its ultrahigh electrical conductivity, high mechanical strength, huge specific surface area and good chemical stability. Graphene is a two-dimensional carbon nanomaterial in a hexagonal honeycomb lattice composed of carbon atoms with sp hybridized orbitals, and exhibits a unique electronic structure due to its atomic-level thickness, thereby exhibiting extraordinary macro-physicochemical characteristics.
However, graphene alone can agglomerate and even re-stack due to van der waals forces and pi-pi stacking, which can seriously affect the applications of graphene. And a fold form is formed on the surface of the graphene, namely, chemical bonds or molecular chain bonds are utilized to form folds at different atomic layers of the graphene or different positions of the same layer, so that stacking and agglomeration of the graphene can be effectively inhibited, and the folded graphene shows more excellent conductivity.
Simple graphene cannot provide effective active sites for adsorption and catalysis processes because the graphene does not contain polar atoms, and doped graphene with heteroatoms such as N, S and the like remarkably changes the electron distribution of the graphene, influences the performances of the graphene such as conductivity, electromagnetism, optics and the like, and can enhance the adsorption effect of the graphene on specific small molecules; if metal atoms can be further loaded in the nitrogen-doped folded graphene, the catalytic and electrochemical properties of the graphene can be greatly changed through the electron transfer and complexation of the nano metal particles or metal atom clusters, and the application of the graphene in the fields of catalysis and energy storage is expanded. Therefore, the metal-loaded nitrogen-doped folded graphene has a very wide application prospect.
The existing methods for preparing the nitrogen-doped folded graphene are more, such as a gel method, a spinning method, a spray drying method and the like, and the methods for loading metal on the folded graphene mainly comprise an impregnation method and the like, but the existing methods generally have the defects of high equipment dependence, complex preparation steps, harsh conditions and the like, and are not beneficial to large-scale preparation, popularization and application of the materials. Therefore, the development of a preparation method of the metal-loaded nitrogen-doped folded graphene, which has the advantages of simple process, strong operability and easiness in large-scale production, has important environmental, economic and social meanings.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a preparation method and application of metal-loaded nitrogen-doped folded graphene, has a simple preparation process, is easy for large-scale production, and has wide market prospects in the aspects of energy storage, catalysis and the like.
The technical scheme of the invention is as follows: a preparation method of metal-loaded nitrogen-doped folded graphene comprises the following steps:
(1) ultrasonically dispersing graphene oxide in a solvent, and stirring to prepare a uniform suspension A;
(2) dissolving ethylenediamine-terminated polyvinylamine in a solvent, adding a metal salt, and stirring to obtain a solution B;
(3) mixing the suspension A and the solution B, and stirring for 5-30 min;
(4) transferring the obtained mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene inner container for hydrothermal reaction, and performing post-treatment to obtain solid powder;
(5) in order to improve the loading strength of some metals, the solid is selectively added into a quartz boat, placed into a tube furnace and calcined under set conditions, and the product is cooled to room temperature to obtain the metal-loaded nitrogen-doped folded graphene.
Further, in the step 1, the addition amount of the graphene oxide is 50-200 mg, the volume of the solvent is 30-50 mL, the stirring time is 5-30 min, and the concentration of the prepared suspension A is 0.05-5 mg/mL.
Further, in the step 2, the addition amount of the ethylenediamine-terminated polyvinylamine is 50-300 mg, the volume of the solvent is 30-50 mL, the concentration of the prepared polyvinylamine solution is 0.05-10 mg/mL, the addition amount of the metal salt is 1-10 mg, and the stirring time is 5-30 min.
Further, the metal salt in step 2 is a metal salt containing any one of the metal elements ruthenium, rhodium, palladium, nickel, cobalt, silver, and copper.
Further, in the step 4, the temperature of the hydrothermal reaction is 150-180 ℃, the heating time is 12-48 hours, and the post-treatment process comprises the steps of firstly centrifuging or filtering the cooled reactant under reduced pressure to collect solid, then washing with pure water and ethanol in sequence, and then drying in vacuum.
Further, when calcining in the step 5, firstly introducing nitrogen for 10-30 min, and introducing an air flow rate of 20-100 mL/min, then heating to 600-900 ℃ at a speed of 2-5 ℃/min, and preserving heat for 60-240 min.
The metal-loaded nitrogen-doped folded graphene prepared by the preparation method can be applied to the aspects of energy storage and catalysis, and particularly can be applied to the aspects of lithium-sulfur battery preparation, catalytic hydrogenation reduction, catalysis of carboxylation reaction based on carbon dioxide and terminal alkyne and the like.
The invention has the beneficial effects that:
1. the metal-loaded nitrogen-doped folded graphene prepared by the method disclosed by the invention has the advantages of large specific surface area, a large number of folds, rich pores, good structure retentivity, uniform nitrogen element doping, uniform loaded metal and small particles, can realize uniform loading of metal quantum dots, greatly changes the catalytic and electrochemical properties of the graphene, and expands the application of the graphene in the fields of catalysis and energy storage;
2. the method has better universality, and can further realize the loading of various metals such as ruthenium, rhodium, palladium, nickel, cobalt, silver and copper on the basis of simply preparing the nitrogen-doped folded graphene;
3. the modification of the multifunctional graphene material is realized by a one-pot method, the experimental process is simple, the operability is strong, and the industrial popularization is facilitated.
Drawings
Fig. 1 is a scanning electron microscope image of nitrogen-doped wrinkled graphene loaded with metallic cobalt prepared in example 3;
fig. 2 is a graph showing the cycling effect of the assembled lithium sulfur battery of example 10 under 2C current density conditions.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1 preparation of nitrogen-doped folded graphene
(1) Ultrasonically dispersing 100 mg of graphene oxide in 40 mL of solvent, and stirring for 20min to prepare uniform suspension;
(2) dissolving 100 mg of ethylenediamine-terminated polyvinylamine (molecular weight 1500) into 40 mL of a solvent, and stirring for 20 min;
(3) mixing the two solutions, stirring for 30 min, transferring into 100 mL hydrothermal reaction kettle with polytetrafluoroethylene liner, heating at 180 deg.C for 36 h, cooling, centrifuging, collecting solid, sequentially washing with pure water and ethanol, and vacuum drying at 60 deg.C to obtain solid powder.
(4) The obtained product is 112 mg of nitrogen-doped graphene with rich folds, and the elemental analysis C: 72.1%, N: 9.1%, H: 4.3%, and a BET test showed a specific surface area of 756 m2/g。
Embodiment 2 preparation of nitrogen-doped folded graphene
(1) Ultrasonically dispersing 100 mg of graphene oxide in 40 mL of solvent, and stirring for 20min to prepare uniform suspension;
(2) dissolving 50 mg of ethylenediamine-terminated polyvinylamine (molecular weight 1500) in 40 mL of a solvent, and stirring for 20 min;
(3) mixing the two solutions, stirring for 30 min, transferring into a 100 mL hydrothermal reaction kettle with a polytetrafluoroethylene inner container, heating at 180 ℃ for 36 h, cooling, centrifuging, collecting solid, sequentially washing with pure water and ethanol, and vacuum drying at 60 ℃ to obtain solid powder;
(4) adding the solid into a quartz boat, placing the quartz boat in a tube furnace, introducing nitrogen for 10-30 min, introducing 50mL/min of air flow speed, heating to 700 ℃ at the speed of 2 ℃/min, preserving heat for 240 min, and cooling to room temperature to obtain the nitrogen-doped graphene with rich folds, wherein the content of the nitrogen-doped graphene is 86 mg, and the elemental analysis C is as follows: 84.5%, N: 5.9%, H: 2.1%, and the BET test showed a specific surface area of 916 m2/g。
Embodiment 3 preparation of metal cobalt-loaded nitrogen-doped folded graphene
(1) Ultrasonically dispersing 100 mg of graphene oxide in 40 mL of solvent, and stirring for 20min to prepare uniform suspension;
(2) dissolving 100 mg of ethylenediamine-terminated polyvinylamine (molecular weight 1500) in 40 mL of a solvent, stirring for 20min, and adding 5 mg of cobalt acetate;
(3) mixing the two solutions, stirring for 30 min, transferring into a 100 mL hydrothermal reaction kettle with a polytetrafluoroethylene inner container, heating at 180 ℃ for 36 h, cooling, centrifuging, collecting solid, sequentially washing with pure water and ethanol, and vacuum drying at 60 ℃ to obtain solid powder;
(4) the obtained product is the metal cobalt-loaded nitrogen-doped folded graphene, and the elemental analysis C: 71.4%, N: 9.7%, H: 4.4%, BET test showed 743 m of specific surface area2The ICP test shows that the loading of the metallic cobalt is 0.67 percent.
Embodiment 4 preparation of metal cobalt-loaded nitrogen-doped folded graphene
(1) Ultrasonically dispersing 100 mg of graphene oxide in 40 mL of solvent, and stirring for 20min to prepare uniform suspension;
(2) dissolving 100 mg of ethylenediamine-terminated polyvinylamine (molecular weight 1500) in 40 mL of a solvent, stirring for 20min, and adding 10 mg of cobalt acetate;
(3) mixing the two solutions, stirring for 30 min, transferring into 100 mL hydrothermal reaction kettle with polytetrafluoroethylene inner container, heating at 180 deg.C for 36 h, cooling, centrifuging, collecting solid, sequentially washing with pure water and ethanol, and vacuum drying at 60 deg.C to obtain solid powder.
(4) The obtained product is the metal cobalt-loaded nitrogen-doped folded graphene, and the elemental analysis C: 73.0%, N: 8.2%, H: 3.7%, and the BET test showed a specific surface area of 807 m2The ICP test shows that the loading of the metallic cobalt is 0.97 percent.
Embodiment 5 preparation of metal nickel-loaded nitrogen-doped folded graphene
(1) Ultrasonically dispersing 100 mg of graphene oxide in 40 mL of solvent, and stirring for 20min to prepare uniform suspension;
(2) dissolving 100 mg of ethylenediamine-terminated polyvinylamine (molecular weight 1500) in 40 mL of a solvent, stirring for 20min, and adding 10 mg of nickel acetate;
(3) mixing the two solutions, stirring for 30 min, transferring into 100 mL hydrothermal reaction kettle with polytetrafluoroethylene inner container, heating at 180 deg.C for 36 h, cooling, centrifuging, collecting solid, sequentially washing with pure water and ethanol, and vacuum drying at 60 deg.C to obtain solid powder.
(4) The obtained product is the metal nickel-loaded nitrogen-doped folded graphene, and the elemental analysis C: 70.7%, N: 9.1%, H: 4.0%, BET test showed 835 m of specific surface area2The ICP test shows that the loading of the metallic nickel is 1.03 percent.
Example 6 preparation of metallic silver-loaded nitrogen-doped folded graphene
(1) Ultrasonically dispersing 100 mg of graphene oxide in 40 mL of solvent, and stirring for 20min to prepare uniform suspension;
(2) dissolving 100 mg of ethylenediamine-terminated polyvinylamine (molecular weight 1500) in 40 mL of a solvent, stirring for 20min, and adding 10 mg of silver nitrate;
(3) mixing the two solutions, stirring for 30 min, transferring into a 100 mL hydrothermal reaction kettle with a polytetrafluoroethylene inner container, heating at 180 ℃ for 36 h, cooling, centrifuging, collecting solid, sequentially washing with pure water and ethanol, and vacuum drying at 60 ℃ to obtain solid powder;
(4) adding the solid into a quartz boat, placing the quartz boat in a tube furnace, introducing nitrogen for 10-30 min, introducing 50mL/min of air flow speed, heating to 700 ℃ at the speed of 2 ℃/min, preserving heat for 180 min, and cooling to room temperature to obtain 93 mg of nitrogen-doped graphene with rich folds, wherein the elemental analysis C is as follows: 85.2%, N: 5.6%, H: 2.2%, the BET test showed a specific surface area of 959 m2The ICP test shows that the loading of the metallic silver is 0.84 percent.
Example 7 preparation of Metal Palladium-Supported Nitrogen-doped Pleated graphene
(1) Ultrasonically dispersing 100 mg of graphene oxide in 40 mL of solvent, and stirring for 20min to prepare uniform suspension;
(2) dissolving 100 mg of ethylenediamine-terminated polyvinylamine (molecular weight 1500) in 40 mL of a solvent, stirring for 20min, and adding 10 mg of palladium chloride;
(3) mixing the two solutions, stirring for 30 min, transferring into a 100 mL hydrothermal reaction kettle with a polytetrafluoroethylene inner container, heating at 180 ℃ for 36 h, cooling, centrifuging, collecting solid, sequentially washing with pure water and ethanol, and vacuum drying at 60 ℃ to obtain solid powder;
(4) adding the solid into a quartz boat, placing the quartz boat in a tube furnace, introducing nitrogen for 10-30 min, introducing 50mL/min of air flow speed, heating to 700 ℃ at the speed of 2 ℃/min, preserving heat for 180 min, and cooling to room temperature to obtain the nitrogen-doped graphene with rich folds, wherein the content of the nitrogen-doped graphene is 101 mg, and the elemental analysis C is as follows: 83.3%, N: 5.1%, H: 1.9%, and the BET test showed a specific surface area of 889 m2The ICP test shows that the loading of the metal palladium is 1.01 percent.
Example 8 metallic silver loaded nitrogen doped corrugated graphene material catalyzed phenylacetylene carboxylation
50 mg of the metal silver-loaded nitrogen-doped pleated graphene prepared in example 6, 5 mL of DMF (dimethyl formamide) as a solvent, 102 mg of phenylacetylene and 0.48 g of cesium carbonate are added into a Schlenk reaction bottle, the reaction bottle is placed in liquid nitrogen to be frozen for 10 min, the atmosphere of the reaction bottle is replaced by carbon dioxide gas three times, and finally carbon dioxide gas (0.1 MPa, balloon) is filled in the reaction bottle, the reaction bottle is heated to room temperature, stirred overnight, the reaction liquid is poured into 50mL of water, the catalyst is recovered, the filtrate is acidified to pH of about 2 by dilute hydrochloric acid, ethyl acetate is extracted for 3 times, organic phases are combined, the organic phases are washed by saturated saline, dried by anhydrous sodium sulfate, and the obtained residue is purified by a prepared thin layer chromatography plate to obtain 88 mg of phenylpropargonic acid with the yield of 61.
Example 9 metallic palladium-loaded nitrogen-doped folded graphene material catalyzes reduction reaction of nitrobenzene
50 mg of the metal palladium-loaded nitrogen-doped folded graphene prepared in example 7 is added into a hydrogenation reaction kettle, 5 mL of methanol is added as a solvent, 1 drop of glacial acetic acid is added, substrate nitrobenzene is added, hydrogen is introduced to 0.5 MPa, gas is replaced for three times, the mixture is stirred at room temperature for 5 hours, and the conversion rate is more than 99%.
Example 10 electrochemical Performance test
(1) Uniformly mixing 100 mg of the metal cobalt-loaded nitrogen-doped folded graphene prepared in example 3 and 100 mg of sulfur powder, grinding for 30 min, placing the obtained mixture in a test tube, and heating for 12 h at 150 ℃;
(2) mixing and uniformly grinding 80 mg of the material obtained in the step 1, 10 mg of polyvinylidene fluoride, 10 mg of conductive carbon black and a few drops of N-methyl pyrrolidone, manually coating the obtained slurry on a clean aluminum foil by using a scraper, and drying the aluminum foil at the temperature of 60 ℃ for 12 hours;
(3) after drying, the coated aluminum foil is cut into positive plates with the diameter of 12 mm by a slicer, and the sulfur carrying capacity of the unit area of the positive plates is about 0.8-1.0 mg/cm2；
(4) Assembling the battery in a glove box (Mikerona) with the water oxygen content less than 1 ppm, adopting a 2016 type battery shell, taking a lithium sheet (with the diameter of 14 mm) as a reference electrode and a counter electrode, and taking a diaphragm type Celgard 2400, wherein the used electrolyte comprises 1M LiTFSI/DME + DOL (volume ratio of 1: 1) mixed ether organic solution added with 2 wt% of lithium nitrate;
(5) the assembled cell was left to stand for 12 hours and placed in a 25 ℃ incubator for electrochemical testing using a blue testing system (LANDCT 2001A).
The battery has an initial discharge specific capacity of 1423.5 mAh/g under the current density of 0.2C (335 mA/g), and after 5 cycles of activation, the battery still maintains 491.8 mAh/g under the current density of 2C (3350 mA/g) after 1000 cycles of circulation.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (7)
1. A preparation method of metal-loaded nitrogen-doped folded graphene is characterized by comprising the following steps:
(1) ultrasonically dispersing graphene oxide in a solvent, and stirring to prepare a uniform suspension A;
(2) dissolving ethylenediamine-terminated polyvinylamine in a solvent, adding a metal salt, and stirring to obtain a solution B;
(3) mixing the suspension A and the solution B, and stirring for 5-30 min;
(4) transferring the obtained mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene inner container for hydrothermal reaction, and performing post-treatment to obtain solid powder;
(5) in order to improve the loading strength of some metals, the solid is selectively added into a quartz boat, placed into a tube furnace and calcined under set conditions, and the product is cooled to room temperature to obtain the metal-loaded nitrogen-doped folded graphene.
2. The method for preparing metal-loaded nitrogen-doped corrugated graphene according to claim 1, wherein in the step 1, the addition amount of graphene oxide is 50-200 mg, the volume of the solvent is 30-50 mL, the stirring time is 5-30 min, and the concentration of the prepared suspension A is 0.05-5 mg/mL.
3. The method for preparing metal-loaded nitrogen-doped folded graphene according to claim 1, wherein in the step 2, the addition amount of the ethylenediamine-terminated polyvinylamine is 50-300 mg, the volume of the solvent is 30-50 mL, the concentration of the prepared polyvinylamine solution is 0.05-10 mg/mL, the addition amount of the metal salt is 1-10 mg, and the stirring time is 5-30 min.
4. The method according to claim 1, wherein the metal salt in step 2 is a metal salt containing any one of the metal elements ruthenium, rhodium, palladium, nickel, cobalt, silver, and copper.
5. The preparation method of metal-loaded nitrogen-doped pleated graphene according to claim 1, wherein in the step 4, the temperature of the hydrothermal reaction is 150-180 ℃, the heating time is 12-48 h, and the post-treatment process comprises the steps of centrifuging or filtering the cooled reactant under reduced pressure to collect solid, washing with pure water and ethanol in sequence, and then drying in vacuum.
6. The method for preparing metal-loaded nitrogen-doped corrugated graphene according to claim 1, wherein during the calcining in the step 5, nitrogen is firstly introduced for 10-30 min, the air flow rate is 20-100 mL/min, then the temperature is raised to 600-900 ℃ at the speed of 2-5 ℃/min, and the temperature is maintained for 60-240 min.
7. The application of the metal-loaded nitrogen-doped corrugated graphene prepared by the preparation method of the metal-loaded nitrogen-doped corrugated graphene according to any one of claims 1 to 6 in energy storage and catalysis is characterized in that the specific applicable fields comprise lithium-sulfur battery preparation, catalytic hydrogenation reduction and catalysis of carboxylation reaction based on carbon dioxide and terminal alkyne.
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