CN112275273B - Graphene oxide-carbon rod composite material - Google Patents
Graphene oxide-carbon rod composite material Download PDFInfo
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- CN112275273B CN112275273B CN202011235065.6A CN202011235065A CN112275273B CN 112275273 B CN112275273 B CN 112275273B CN 202011235065 A CN202011235065 A CN 202011235065A CN 112275273 B CN112275273 B CN 112275273B
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J35/40—
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- B01J35/615—
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- B01J35/647—
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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
- 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
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a graphene oxide-carbon rod composite material, wherein the carbon rod is used as an intercalation agent of graphene, can effectively separate agglomeration of graphene oxide, remarkably improves the specific surface area of the graphene oxide, can be used as a catalyst carrier, and is particularly suitable for gas-solid phase catalytic reaction.
Description
Technical Field
The invention relates to a graphene oxide-carbon rod composite material and a preparation method thereof, belongs to the field of preparing carbon materials by using templates, and particularly relates to the field of preparing nano carbon materials by using an electrochemical anodic oxidation method.
Technical Field
The hydrogen energy is used as a novel efficient, clean and renewable resource, and the main preparation method is through hydrocarbon reforming and water gas shift reaction. Due to the thermodynamic limitations of the process, the hydrogen-rich gas produced always contains 0.5-2vol.% CO. In general, the electrode material of the fuel cell is Pt, and the presence of CO in the reformed gas not only poisons the Pt electrode, but also is more easily adsorbed on the surface of the catalyst, further preventing the catalytic oxidation of the fuel, so that the content of CO in the hydrogen-rich gas must be limited to less than 100 ppm. Carbon monoxide preferential oxidation is one of the most effective methods for purifying CO in hydrogen-rich gases.
The reported preferential oxidation catalysts for high efficiency CO mainly include noble metal (Pt, ru, rh, pd, ir etc.) catalysts, oxide catalysts (CuO-CeO 2), gold-based catalysts. Among them, platinum-based bimetallic catalysts have been widely focused on their excellent activity, higher selectivity and stability, such as Pt-Co/SiO2, pt-Ni/Al2O3, pt-La/mordenite, pt-Fe/CeO2, and Pt-alkali metal/Al 2O3 bimetallic catalysts all exhibit excellent catalytic activity. Such as: the Pt-Co bimetallic catalyst prepared by Li can effectively widen the window of complete CO conversion under the condition of high space velocity of 120,000 ml/g.h. Also, chin finds that the Pt-Ru/SiO2 catalyst has extremely high activity and stability at a low temperature stage, and Schubert also reports that the existence of Sn can remarkably improve the stability of Pt and the high-temperature selectivity of the catalyst in the CO preferential oxidation process.
At present, a series of carbon-based composite materials, such as activated carbon, graphite fibers, carbon nanotubes and graphene, are regarded as excellent carriers for research due to their excellent mechanical properties, heat conducting properties and chemical properties. Kumari grows multi-wall carbon nanotubes on the surface of alumina by a vapor deposition method, and then prepares various CNT-Al2O3 compounds by a spark plasma sintering method. Worsley prepared a series of SWNT/oxide (SiO 2, snO2, tiO 2) monolithic composites by depositing oxides on the surface of carbon nanotube carbon aerogel. Moreover, graphene-based catalysts are widely used in the catalytic field, but focus on some liquid-phase catalytic reactions. Truong-Huu uniformly disperses palladium (Pd) nanoparticles onto the surface of single-layer graphene, and is applied to liquid phase selective c=c hydrogenation reaction. The high-efficiency hydrogenation activity is mainly used in a liquid phase, and the single-layer uniformly dispersed 2D graphene structure has extremely high surface area, interface and edge adsorbability. However, the problem of the sizing of the graphene-based carbon nanotube catalyst (such as easy shedding and stripping of the carbon nanotubes on the carrier, the fact that the active particles are wrapped between large graphene layers and cannot contact with gas phase, etc.) is difficult to solve, and the application of the novel carbon material in gas-solid phase catalytic reaction, such as CO-PROX reaction, is severely limited.
According to the above, it is obvious that when graphene is used as a catalyst carrier in the prior art, the graphene is mainly used as a doping agent, which is equivalent to using graphene modified silicon oxide, aluminum oxide or titanium oxide, and there is a problem that graphene is directly used as a gas-solid phase catalyst carrier, mainly because due to the defects of hummer, it is difficult to obtain single-layer or < 100 layers of graphene, even if single-layer graphene is obtained, the single-layer graphene can only exist in a small amount and cannot be obtained in a large amount, stacking and agglomeration of graphene sheets can occur more when the graphene is dried, and when the graphene is used as a catalyst carrier, an active component is clamped in the middle of the graphene sheets, so that gas cannot contact with the active component in the graphene, and therefore, in the prior art, there is a problem that graphene solid is directly used as a carrier, such as a graduation paper: the novel carbon material composite catalyst is used for preparing graphene through hummer and then loading active component Pt on the graphene, and is used for CO complete oxidation reaction as recorded in the prior art of CO preferential oxidation and CO complete oxidation reaction under hydrogen atmosphereThe feed gas composition was 1vol.% CO, 10vol.% O2, and 89vol.% N2. ) At 100-175 o The activity of C is only 30%, the reaction activity is extremely low under such superior reaction conditions, and under the severe conditions of prior preferential oxidation of 1vol.% CO,1vol.% O2, 50vol.% H2 and 48vol.% N2, or under the conditions of 1vol.% CO,1vol.% O2,12.5vol.% CO2,15 vol.% H2O,50vol.% H2 and N2 equilibrium gas used by the actual industry, the catalytic reaction fear is less than 10%, namely, the problem of agglomeration or interlayer agglomeration of graphene materials severely limits the application of graphene in the field of catalyst carriers.
Disclosure of Invention
Based on the limitation of the graphene in practical use caused by the agglomeration problem in the prior art, the invention provides a graphene oxide-carbon rod composite material and a preparation method thereof, wherein the carbon rods are intercalated between graphene oxide sheets, the length of the carbon rods is 10-20 mu m, the diameter is 0.5-0.7 mu m, and the specific surface area of the graphene oxide-carbon rod composite material is 289g-357m 2 And/g, the mesoporous aperture is 5-10nm.
The preparation method of the graphene oxide-carbon rod composite material comprises the following steps:
(1) Preparation of 20-25wt.% graphene oxide aqueous solution by hummer method by adding 25ml concentrated sulfuric acid into a dry four-necked flask, and cooling to 0-2 with ice bath o C, adding 0.5g of natural crystalline flake graphite and 0.5g of NaNO into the mixture while stirring 3 And slowly add 3g KMnO 4 Particles, this stage being a low temperature reaction. Then placing the flask in a constant-temperature water bath at about 35 ℃, and continuously stirring for 4 hours when the temperature of the reaction liquid is raised to about 35 ℃, thus completing the medium-temperature reaction. Then 46ml of deionized water was slowly added to the solution at 98 o Stirring for 15min at C, adding 140ml deionized water and 3ml H after high temperature reaction 2 O 2 (30 wt.%) 40min of reaction. And finally, washing the graphite oxide solution with deionized water for a plurality of times to neutrality.
(2) Preparing 10-15wt.% of an aqueous carbon rod solution:
(a) Forming a porous oxide film on the surface of an aluminum material by using the aluminum material as a base material through an electrochemical method;
(b) Repeatedly filling the carbon source into the oxide film pore canal for many times by taking the porous oxide film as a hard template and taking the asphalt resin polymer as a carbon source;
(c) Mechanically polishing the material obtained in step (2);
(d) Etching the material obtained in the step (3) by strong acid to remove the hard template;
(e) Washing, drying and dissolving to obtain the carbon rod aqueous solution.
(3) Introducing the carbon rod aqueous solution in the step (2) into the graphene oxide aqueous solution in the step (1), and performing auxiliary ultrasonic stirring treatment;
(4) And (5) performing freeze drying treatment to obtain the graphene oxide-carbon rod composite material.
Further, the substrate is pretreated: degreasing-washing-pickling-washing-alkaline etching-washing-polishing-washing, wherein the degreasing solution: 45g/L sodium bicarbonate, 45g/L sodium carbonate, and a temperature of 40% o C, performing operation; pickling solution: 0.02g/L of hydrofluoric acid, 4g/L of sulfuric acid, 1g/L of surfactant, room temperature, alkaline etching solution: 45g/L sodium hydroxide, 1g/L sodium gluconate, temperature 40 o C, the time is 2-3min; light-emitting liquid: 350g/L nitric acid solution for 2-3min.
Further, the process of the step (1) is as follows: taking aluminum or aluminum alloy as a base material, taking an inert lead material as a cathode, taking 10-20wt.% sulfuric acid aqueous solution as electrolyte, and the current density is 1-2A/dm 2 For 30-100min at 20-30 o C, obtaining anodic oxide film aluminum material, and subjecting the obtained anodic oxide film aluminum material to 35 o And C, reaming with 5-7wt.% phosphoric acid for 40-50min, and vacuum drying, wherein the thickness of the oxide film is 10-20 micrometers, and the pore diameter is 0.5-0.7 micrometers.
Further, the preparation method of the asphalt resin polymer in the step (2) comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-necked bottle, evacuating with nitrogen, and cooling at 135 o C, obtaining a black asphalt resin product under the continuous stirring condition, repeatedly washing, filtering and drying by using propanol to obtain a light yellow powder solid, dissolving the light yellow powder in tetrahydrofuran, stirring for 30min, and then adding the reamed oxygen obtained in the step (1)Continuously stirring the film-formed aluminum material, performing auxiliary vacuumizing to 10-20Pa, filling for 12-24h, and performing rotary evaporation to obtain light yellow oxide film aluminum material, and further mixing with nitrogen atmosphere at 800 deg.F o Carbonizing for 4h under C.
Further, the mechanical polishing is polishing by a polishing wheel and is used for removing the non-pore carbon materials on the anodic oxide film porous layer.
Further, the strong acid is 15wt.% H 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, under stirring at 100 o C, reflux treatment for 3h.
Further, the ultrasound parameters: the ultrasonic frequency is 40-50 KHz, the ultrasonic power is 500-600W, and the ultrasonic time is 1-3h.
Further, the stirring parameters: the stirring speed is 180-500 r/min, the stirring time is 1-3h, and the stirring temperature is 30-50 o C。
Further, the drying pressure of the vacuum freeze drying is 5-10Pa, the cold well temperature is-20 to-60 ℃ and the time is 24-48h.
Regarding the preparation method:
(1) hummer preparation of graphene oxide: into a dry four-necked flask, 25ml of concentrated sulfuric acid was added, and the flask was cooled to 0 to 2 with an ice bath o C, adding 0.5g of natural crystalline flake graphite and 0.5g of NaNO into the mixture while stirring 3 And slowly add 3g KMnO 4 Particles, this stage being a low temperature reaction. Then placing the flask in a constant-temperature water bath at about 35 ℃, and continuously stirring for 4 hours when the temperature of the reaction liquid is raised to about 35 ℃, thus completing the medium-temperature reaction. Then 46ml of deionized water was slowly added to the solution at 98 o Stirring for 15min at C, adding 140ml deionized water and 3ml H after high temperature reaction 2 O 2 (30 wt.%) 40min of reaction. Finally, the graphite oxide solution is washed to be neutral for many times by deionized water, which is a typical low-temperature-medium-temperature-high-temperature hummer method, and the invention does not exclude other methods for preparing graphene oxide in the prior art, only exemplary description is made here, and the obtained graphene oxide sheet is thinner, as shown in fig. 8.
(2) With respect to preparing 10-15wt.% carbon rod aqueous solution:
as shown in fig. 1, the substrate is subjected to pretreatment-anodic oxidation to prepare a hard template, filling-polishing-corrosion to finally obtain the nano carbon rod.
(a) Regarding the pretreatment: regardless of the surface treatment process, to obtain a good effect, cleaning the surface is a primary condition, the application hopes to obtain an anodic oxide film with uniform nano pore channels and uniform thickness, so that the substrate is pretreated to obtain the basis of the uniform oxide film in all directions: degreasing, water washing, acid washing, water washing, alkali etching, water washing, light emitting and water washing.
Wherein the degreasing solution: 45g/L sodium bicarbonate, 45g/L sodium carbonate, and a temperature of 40% o And C, removing greasy dirt on the surface of the workpiece before surface treatment, ensuring the bonding strength of the conversion film and the matrix metal, ensuring the smooth progress of chemical reaction of the conversion film, and obtaining the conversion film layer with qualified quality.
Pickling solution: 0.02g/L of hydrofluoric acid, 4g/L of sulfuric acid, 1g/L of surfactant, room temperature, acid washing to remove dirt and oxide on the surface, and no hydrogen embrittlement, wherein the acid degreasing mechanism of the aluminum alloy is as follows: and (3) dissolving out the oxide on the aluminum surface to loosen the greasy dirt, and separating the greasy dirt from the metal surface by utilizing the action of water flow.
Alkaline etching solution: 45/g/L sodium hydroxide, 1/g/L sodium gluconate, temperature 40 o C, the time is 2-3min, the aluminum alloy workpiece cannot be subjected to conversion film treatment after degreasing process, the surface of the aluminum alloy workpiece generally has the defects of natural oxide film, processing stripes and the like, and the aluminum alloy workpiece needs to be subjected to corrosion treatment to remove the natural oxide film and activate the surface. Alkaline etching is the most commonly used etching process, and the main component is NaOH solution, which has low cost and easy maintenance and management, and is used for removing oxide films which cannot be removed by acid washing.
Light-emitting liquid: 350g/L nitric acid solution for 2-3min. The surface of the workpiece subjected to acid-base corrosion is usually darkened because of the existence of copper oxide on the surface of the aluminum alloy with higher copper content, so that black ash is formed. In order to make the surface of the workpiece bright, the polishing treatment is usually carried out in a nitric acid solution.
(b) With respect toAnodic oxidation: 10-20wt.% sulfuric acid aqueous solution is adopted as electrolyte, and the current density is 1-2A/dm 2 For 30-100min at 20-30 o C, the thickness of the obtained anodic oxide film aluminum material is 10-20 micrometers, the pore diameter is concentrated below 500nm, and the pore diameter is smaller, as shown in figure 5, the pore diameter is unfavorable for the subsequent carbon filling precursor, so that the obtained anodic oxide film aluminum material is 35 percent o And C, reaming is carried out by using 5-7wt.% of phosphoric acid for 40-50min, and vacuum drying is carried out to finish reaming of the anodic oxide film pore canal, so that filling of a carbon precursor is facilitated, the thickness is not obviously reduced or the reduction is not obvious in the reaming process, the pore diameter is enlarged to 0.5-0.7 mu m, as shown in figure 6, the anodic oxide film pore canal hard template for reaming for 20min is obtained, as shown in figure 7, and the anodic oxide film hard template for reaming for 45min is obtained.
(c) Regarding the preparation of the precursor: the principle of selecting the carbon precursor is that the molecular size is suitable for entering the pore canal of the anodic oxide film template, the compatibility (wettability and hydrophilicity) with the pore wall is good, and the carbonization yield is higher after separating or further polymerizing substances in the pore is good. Currently, carbon precursors are mainly sucrose, xylose, glucose, furfuryl alcohol resins, phenolic resins, mesophase pitch, anthracene, phenanthrene, divinylbenzene, and some organic solvents such as ethanol, methanol, toluene, and the like. There are also a number of methods for introducing different precursors into the channels of a hard template, the most common being mainly solution impregnation, the type of carbon precursor having a large influence on the structure of the final resulting carbon material. Furfuryl alcohol is used as a carbon precursor, so that mesoporous carbon with good order is easily prepared; when the mesophase pitch is used as a carbon precursor, the microporosity of the material can be obviously reduced, and the carbon yield is high; in addition, the type of carbon precursor has a very important influence on the graphitization degree of the finally obtained carbon material, and precursors with loose molecular structures (such as phenolic resin) with high oxygen content can obtain hard carbon materials with a large number of micropores and higher oxygen content after carbonization, and the hard carbon materials are difficult to graphitize. The mesoporous carbon material with higher graphitization degree can be obtained after carbonization of the precursor (such as anthracene) with condensed ring structure and without oxygen, and the carbon filler of the invention hopes the microporosity of the carbon material and has high carbon yield, so that the pitch resin polymer is used for filling.
The preparation method comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-necked bottle, evacuating with nitrogen, and cooling at 135 o C, obtaining a black asphalt resin product under the continuous stirring condition, repeatedly washing, filtering and drying by using propanol to obtain a pale yellow powder solid, dissolving the pale yellow powder in tetrahydrofuran, stirring for 30min, then adding the reamed oxide film aluminum material obtained in the step (1), continuously stirring, carrying out auxiliary vacuumizing, filling for 12-24h, then carrying out rotary evaporation to obtain the pale yellow oxide film aluminum material, and further carrying out nitrogen atmosphere with 800 percent o Carbonizing for 4h under C.
In the process, the temperature and the water are needed to be paid attention to in the filling process (a), so that the water-based hole sealing phenomenon of the anodic oxide film is avoided, and the filling of the carbon precursor liquid is obviously reduced due to the hole sealing; (b) Stirring and vacuumizing are necessary means, and because of the viscosity of the asphalt polymer, the filling process is slightly difficult, so that stirring is necessary at all times, vacuumizing is performed, and the carbon precursor is assisted to enter a pore channel, and then evaporation, drying and carbonization processes are performed; (c) The filling times are determined according to the needs, and the filling is not performed as much as possible.
In addition, the quality of the anodic oxidation porous film hard template, the carbon precursor filling amount and the carbonization process all affect the mesostructure of the nano carbon rod to a great extent. Of particular importance is the selection of the carbon precursor. The carbon precursor molecules can interact with the template molecules to form ordered mesostructures. Secondly, the precursor molecules must also be capable of cross-linking themselves to form a thermoset polymer network, which can be used to resist deformation caused by shrinkage of the framework during high temperature carbonization and template removal in template removal engineering. In addition, different carbon precursors undergo different carbonization processes, so that the mesostructure of the carbon rod can be influenced, and the microstructure such as graphitization degree and the like can be also influenced. Therefore, the carbon precursor molecules are required to have the characteristics of proper size, good thermal stability, abundant warp groups, high carbon residue of the polymer, and the like.
(d) Regarding polishing: mechanical polishing is a key step for controlling morphology of the invention, as shown in fig. 1, when excessive carbon precursor is filled, carbon materials are attached to the surface of the anodic oxide film, polishing by a polishing wheel is needed at the moment and used for removing the carbon materials in non-pore channels on the porous layer of the anodic oxide film, one end of the finally obtained carbon rod is a semicircular arc section of the position of the barrier layer of the anodic oxide film, and one end is a mechanically polished flat line end, as shown in fig. 2, wherein one end is arc-shaped and the other end is flat line end.
(e) Regarding corrosion, in the case of anodized aluminum, the base materials are aluminum oxide and aluminum, and because of the amphoteric nature of aluminum, it is possible to use an acidic solution or an alkaline solution for corrosion, but the present application abandons alkaline corrosion because the present invention requires the introduction of a large amount of hydrophilic radicals such as hydroxyl groups, oxy groups, etc. on the surface of a carbon material in addition to the removal of the aluminum template, and only alkaline corrosion is insufficient, and thus a strong acid of 15wt.% H is used 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, under stirring at 100 o And C, carrying out reflux treatment 3h, namely, introducing hydroxyl through strong acid corrosion and reflux treatment, so that the water solubility of the carbon material is improved, and under an ethanol and water solution system, as shown in an SEM (scanning electron microscope) of a drawing 2, the carbon rod is uniformly dispersed and has low polymerization, and the application field of the carbon rod is remarkably widened due to the existence of the dispersion state.
As shown in fig. 3 and 4, the regular carbon rod material obtained after direct corrosion without polishing is shown in top view and side view.
(3) Regarding mixing: the graphene oxide aqueous solution with 20-25wt.% prepared by a hummer method and the carbon rod aqueous solution with 10-15wt.% prepared by a template method are directly mixed, and the mutual addition is not obviously different, and the key is that ultrasonic and stirring treatment is carried out, and the dispersibility of the graphene oxide in the aqueous solution is better, so that the graphene oxide prepared by the hummer method is directly used as a reactant without drying treatment; by adding ultrasound and stirring: under the conditions that the ultrasonic frequency is 40-50 KHz and the ultrasonic power is 500-600W, the ultrasonic time is 1-3h; stirring speed is 180-500 r/min, stirring time is 1-3h, stirring is carried outAt a temperature of 30-50 DEG C o C, can be showing further dispersion graphite alkene lamella to be favorable to graphite carbon rod to disperse between the graphite alkene lamella, as shown in TEM of figure 9, there is black carbon rod to exist between two flaky graphene oxides, the carbon rod is shown as the intercalating agent can effectual dispersion graphite alkene lamella, as shown in figure 10, partial carbon rod has obviously jacked the graphite alkene lamella for the effectual dispersion of graphite alkene lamella.
(4) Regarding vacuum freeze drying: the drying technology is necessary and irreplaceable, and can effectively avoid re-agglomeration of graphene because the actual state of the carbon material in the aqueous solution can be remarkably maintained by vacuum freeze-drying, if the technologies of forced air drying, spin drying, evaporating drying and the like are used, the carbon composite material is found to be sticky and attached to the surface of a drying vessel, and the carbon composite material is freeze-dried, is flocculent in the drying vessel and can be directly poured out of the drying vessel, so that the structural form of the graphene-carbon rod composite material is effectively maintained, the drying pressure of the vacuum freeze-drying is 5-10Pa, the cold well temperature is-20 to-60 ℃, and the time is 24-48h.
The scheme of the invention has the following beneficial effects:
(1) The size, the size and the shape of the carbon rod prepared by the template method are almost consistent.
(2) The nano carbon rods are highly dispersed and uniform in all directions.
(3) The carbon rod can be used for graphene dispersion intercalation agent, can be used as raw material of carbon material electrode, can be used as catalyst carrier, and has wide application field.
(4) The carbon rod intercalation agent can obviously improve the specific surface area of the graphene material and provide a reaction place for gas-solid phase catalytic reaction.
Drawings
FIG. 1 is a schematic diagram of a carbon nanomaterial fabrication method according to the present invention.
Fig. 2 is a TEM image of the inventive nanocarbon stick under water-ethanol conditions.
Fig. 3 is a SEM plan view of the nanorod-shaped carbon material without polishing according to the present invention.
Fig. 4 is a side view of a polished nanorod-shaped carbon material of the present invention.
Fig. 5 is an SEM image of the pore channels of the un-reamed anodic oxide film of the invention.
FIG. 6 is an SEM image of an anodized film hole drilled for 20 minutes according to the present invention.
Fig. 7 is an SEM image of anodic oxide film pore canal reamed for 45min according to the present invention.
Fig. 8 is an SEM image of graphene prepared by the hummer method according to the present invention.
Fig. 9 is a TEM image of a graphene-carbon rod composite of the present invention.
Fig. 10 is an SEM image of the graphene-carbon rod composite of the present invention.
FIG. 11 is an N-type graphene-carbon rod composite material according to the present invention 2 Physical adsorption desorption isotherms.
Fig. 12 is a BJH pore size distribution line of the graphene-carbon rod composite material of the present invention.
Detailed Description
Example 1
The preparation method of the graphene oxide-carbon rod composite material comprises the following processing steps:
(1) 20wt.% graphene oxide aqueous solution was prepared by the hummer method.
(2) 10wt.% of an aqueous carbon rod solution was prepared:
(a) Pretreatment: degreasing, washing, pickling, washing, alkali etching, washing, light emitting and washing the aluminum material in sequence, wherein the degreasing solution is as follows: 45g/L sodium bicarbonate, 45g/L sodium carbonate, and a temperature of 40% o C, performing operation; pickling solution: 0.02g/L of hydrofluoric acid, 4g/L of sulfuric acid, 1g/L of surfactant, room temperature, alkaline etching solution: 45/g/L sodium hydroxide, 1/g/L sodium gluconate, temperature 40 o C, the time is 2min; light-emitting liquid: 350g/L nitric acid solution for 2 min.
(b) The aluminum material is used as a base material, a porous oxide film is formed on the surface of the aluminum material by an electrochemical method, the pretreated aluminum material is used as an anode, an inert lead material is used as a cathode, 10wt.% sulfuric acid aqueous solution is used as electrolyte, and the current density is 1A/dm 2 The time is 30min,temperature 20 o C, obtaining anodic oxide film aluminum material, and subjecting the obtained anodic oxide film aluminum material to 35 o Reaming was performed with 5wt.% phosphoric acid for 40min and vacuum drying.
(c) The porous oxide film is used as a hard template, the asphalt resin polymer is used as a carbon source, the carbon source is repeatedly filled in the pore canal of the oxide film for many times, and the preparation method of the asphalt resin polymer comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-necked bottle, evacuating with nitrogen, and cooling at 135 o C, obtaining a black asphalt resin product under the continuous stirring condition, repeatedly washing, filtering and drying by using propanol to obtain a pale yellow powder solid, dissolving the pale yellow powder in tetrahydrofuran, stirring for 30min, then adding the reamed oxide film aluminum material obtained in the step (1), continuously stirring, carrying out auxiliary vacuumizing until the vacuum degree is 10Pa, filling for 12h, and then carrying out rotary evaporation to obtain the pale yellow oxide film aluminum material, and further carrying out nitrogen atmosphere with 800 o Carbonizing for 4h under the condition of C, wherein the filling times are 2 times;
(d) Mechanically polishing the material obtained in the step (2): the mechanical polishing is polishing by a polishing wheel and is used for removing the non-pore carbon materials on the anodic oxide film porous layer.
(e) Etching the material obtained in the step (3) by strong acid to remove the hard template: the strong acid is 15wt.% H 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, under stirring at 100 o C reflux treatment 3h.
(f) Washing, drying and dissolving to obtain a carbon rod aqueous solution: washing with deionized water for several times to neutral, filtering, and drying to 60 o And C, air drying 12 h.
(3) Introducing the carbon rod aqueous solution in the step (2) into the graphene oxide aqueous solution in the step (1), and performing auxiliary ultrasonic stirring treatment: ultrasonic parameters: under the conditions of 40KHz ultrasonic frequency and 500W ultrasonic power, the ultrasonic time is 1h. . Stirring parameters: stirring speed is 180r/min, stirring time is 1h, and stirring temperature is 30 o C。
(4) And (3) freeze-drying to obtain the graphene oxide-carbon rod composite material, wherein the drying pressure of vacuum freeze-drying is 5-10Pa, the cold well temperature is-20 to-60 ℃, and the time is 24 hours.
Example 2
The preparation method of the graphene oxide-carbon rod composite material comprises the following processing steps:
(1) 22.5wt.% graphene oxide aqueous solution was prepared by the hummer method.
(2) 12.5wt.% carbon rod aqueous solution was prepared:
(a) Pretreatment: degreasing, washing, pickling, washing, alkali etching, washing, light emitting and washing the aluminum material in sequence, wherein the degreasing solution is as follows: 45g/L sodium bicarbonate, 45g/L sodium carbonate, and a temperature of 40% o C, performing operation; pickling solution: 0.02g/L of hydrofluoric acid, 4g/L of sulfuric acid, 1g/L of surfactant, room temperature, alkaline etching solution: 45/g/L sodium hydroxide, 1/g/L sodium gluconate, temperature 40 o C, the time is 2.5min; light-emitting liquid: 350g/L nitric acid solution for 2.5 min.
(b) The aluminum material is used as a base material, a porous oxide film is formed on the surface of the aluminum material by an electrochemical method, the pretreated aluminum material is used as an anode, an inert lead material is used as a cathode, 15wt.% sulfuric acid aqueous solution is used as electrolyte, and the current density is 1.5A/dm 2 For 30-100min at 25 o C, obtaining anodic oxide film aluminum material, and subjecting the obtained anodic oxide film aluminum material to 35 o Reaming was performed with 6wt.% phosphoric acid for 45min and vacuum drying.
(c) The porous oxide film is used as a hard template, the asphalt resin polymer is used as a carbon source, the carbon source is repeatedly filled in the pore canal of the oxide film for many times, and the preparation method of the asphalt resin polymer comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-necked bottle, evacuating with nitrogen, and cooling at 135 o C, obtaining a black asphalt resin product under the continuous stirring condition, repeatedly washing, filtering and drying by using propanol to obtain a pale yellow powder solid, dissolving the pale yellow powder in tetrahydrofuran, stirring for 30min, then adding the reamed oxide film aluminum material obtained in the step (1), continuing stirring, carrying out auxiliary vacuumizing until the vacuum degree is 10-20Pa, filling for 18h, then carrying out rotary evaporation to obtain the pale yellow oxide film aluminum material,further with nitrogen atmosphere, 800 o Carbonizing for 4h under the condition of C, wherein the filling times are 2 times;
(d) Mechanically polishing the material obtained in the step (2): the mechanical polishing is polishing by a polishing wheel and is used for removing the non-pore carbon materials on the anodic oxide film porous layer.
(e) Etching the material obtained in the step (3) by strong acid to remove the hard template: the strong acid is 15wt.% H 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, under stirring at 100 o C reflux treatment 3h.
(f) Washing, drying and dissolving to obtain a carbon rod aqueous solution: washing with deionized water for several times to neutral, filtering, and drying to 60 o And C, air drying 12 h.
(3) Introducing the carbon rod aqueous solution in the step (2) into the graphene oxide aqueous solution in the step (1), and performing auxiliary ultrasonic stirring treatment: ultrasonic parameters: under the conditions that the ultrasonic frequency is 45KHz and the ultrasonic power is 550W, the ultrasonic time is 2h. Stirring parameters: stirring speed is 300r/min, stirring time is 2h, and stirring temperature is 40 o C。
(4) And (3) freeze-drying to obtain the graphene oxide-carbon rod composite material, wherein the drying pressure of vacuum freeze-drying is 5-10Pa, the cold well temperature is-20 to-60 ℃, and the time is 36h.
Example 3
The preparation method of the graphene oxide-carbon rod composite material comprises the following processing steps:
(1) 25wt.% graphene oxide aqueous solution was prepared by the hummer method.
(2) 15wt.% of an aqueous carbon rod solution was prepared:
(a) Pretreatment: degreasing, washing, pickling, washing, alkali etching, washing, light emitting and washing the aluminum material in sequence, wherein the degreasing solution is as follows: 45g/L sodium bicarbonate, 45g/L sodium carbonate, and a temperature of 40% o C, performing operation; pickling solution: 0.02g/L of hydrofluoric acid, 4g/L of sulfuric acid, 1g/L of surfactant, room temperature, alkaline etching solution: 45/g/L sodium hydroxide, 1/g/L sodium gluconate, temperature 40 o C, the time is 2-3min; light-emitting liquid:350g/L nitric acid solution for 3min.
(b) The aluminum material is used as a base material, a porous oxide film is formed on the surface of the aluminum material by an electrochemical method, the pretreated aluminum material is used as an anode, an inert lead material is used as a cathode, 20wt.% sulfuric acid aqueous solution is used as electrolyte, and the current density is 2A/dm 2 For 100min at 30 o C, obtaining anodic oxide film aluminum material, and subjecting the obtained anodic oxide film aluminum material to 35 o Reaming was performed with 7wt.% phosphoric acid for 50min and vacuum drying.
(c) The porous oxide film is used as a hard template, the asphalt resin polymer is used as a carbon source, the carbon source is repeatedly filled in the pore canal of the oxide film for many times, and the preparation method of the asphalt resin polymer comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-necked bottle, evacuating with nitrogen, and cooling at 135 o C, obtaining a black asphalt resin product under the continuous stirring condition, repeatedly washing, filtering and drying by using propanol to obtain a pale yellow powder solid, dissolving the pale yellow powder in tetrahydrofuran, stirring for 30min, then adding the reamed oxide film aluminum material obtained in the step (1), continuously stirring, carrying out auxiliary vacuumizing until the vacuum degree is 10-20Pa, filling for 24h, and then carrying out rotary evaporation to obtain the pale yellow oxide film aluminum material, and further carrying out nitrogen atmosphere with 800 ℃ to obtain the product o Carbonizing for 4h under the condition of C, wherein the filling times are 2 times;
(d) Mechanically polishing the material obtained in the step (2): the mechanical polishing is polishing by a polishing wheel and is used for removing the non-pore carbon materials on the anodic oxide film porous layer.
(e) Etching the material obtained in the step (3) by strong acid to remove the hard template: the strong acid is 15wt.% H 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, under stirring at 100 o C reflux treatment 3h.
(f) Washing, drying and dissolving to obtain a carbon rod aqueous solution: washing with deionized water for several times to neutral, filtering, and drying to 60 o And C, air drying 12 h.
(3) Introducing the carbon rod aqueous solution in the step (2) into the oxygen in the step (1)In the graphene water solution, auxiliary ultrasonic stirring treatment: ultrasonic parameters: the ultrasonic frequency is 50KHz, and the ultrasonic power is 600W, and the ultrasonic time is 1-3h. . Stirring parameters: the stirring speed is 500r/min, the stirring time is 3h, and the stirring temperature is 50 o C。
(4) And (3) freeze-drying to obtain the graphene oxide-carbon rod composite material, wherein the drying pressure of vacuum freeze-drying is 5-10Pa, the cold well temperature is-20 to-60 ℃, and the time is 48 hours.
Comparative example 1
Into a dry four-necked flask, 25ml of concentrated sulfuric acid was added, and the flask was cooled to 0 to 2 with an ice bath o C, adding 0.5g of natural crystalline flake graphite and 0.5g of NaNO into the mixture while stirring 3 And slowly add 3g KMnO 4 Particles, this stage being a low temperature reaction. Then placing the flask in a constant-temperature water bath at about 35 ℃, and continuously stirring for 4 hours when the temperature of the reaction liquid is raised to about 35 ℃, thus completing the medium-temperature reaction. Then 46ml of deionized water was slowly added to the solution at 98 o Stirring for 15min at C, adding 140ml deionized water and 3ml H after high temperature reaction 2 O 2 (30 wt.%) for 40min, then deionized, repeatedly washing acetone to neutrality, and drying in a blast furnace at 40-50 deg.C.
The preparation method of graphene oxide used in the above examples 1 to 3 was exactly the same as that of comparative example 1, and the graphene obtained in example 2 and comparative example 1 were compared, as shown in N of FIG. 11 2 Physical adsorption and desorption isotherms, BJH pore size distribution line shown in FIG. 12, wherein specific surface area, pore volume and mesopore size are summarized as follows.
TABLE 1
The results show that the specific surface area of the graphene oxide can be remarkably improved by using the carbon rod as an intercalation agent, and the pore size distribution and pore volume results of the comparative example 1 show that the carbon rod as the intercalation agent effectively expands the graphene, the pore size is enlarged, the pore volume is improved, and a necessary reaction place is provided for the graphene oxide-carbon rod composite material as a gas-solid phase catalytic reaction.
Although the present invention has been described by way of example with reference to the preferred embodiments, the present invention is not limited to the specific embodiments, and may be modified appropriately within the scope of the present invention.
Claims (10)
1. A graphene oxide-carbon rod composite material is characterized in that carbon rods are intercalated between graphene oxide sheets, wherein the length of each carbon rod is 10-20 mu m, the diameter of each carbon rod is 0.5-0.7 mu m, and the specific surface area of the graphene oxide-carbon rod composite material is 289-357m 2 And/g, wherein the mesoporous aperture is 5-10nm, the graphene oxide is prepared by a hummer method, and the carbon rod is prepared by the following method:
(1) Forming a porous oxide film on the surface of an aluminum material by using the aluminum material as a base material through an electrochemical method;
(2) Repeatedly filling the carbon source into the oxide film pore canal for many times by taking the porous oxide film as a hard template and taking the asphalt resin polymer as a carbon source;
(3) Mechanically polishing the material obtained in step (2);
(4) Etching the material obtained in the step (3) by strong acid to remove the hard template;
(5) Washing, drying and dissolving to obtain the carbon rod aqueous solution.
2. A graphene oxide-carbon rod composite material according to claim 1, wherein the substrate is pretreated: degreasing-washing-pickling-washing-alkaline etching-washing-polishing-washing, wherein the degreasing solution: 45g/L of sodium bicarbonate, 45g/L of sodium carbonate and the temperature is 40 ℃; pickling solution: 0.02g/L of hydrofluoric acid, 4g/L of sulfuric acid, 1g/L of surfactant and room temperature; alkaline etching solution: 45g/L of sodium hydroxide, 1g/L of sodium gluconate, and the temperature is 40 ℃ for 2-3min; light-emitting liquid: 350g/L nitric acid solution for 2-3min.
3. A graphite oxide as claimed in claim 1The alkene-carbon rod composite material is characterized in that the process of the step (1) is as follows: taking aluminum or aluminum alloy as a base material, taking an inert lead material as a cathode, taking 10-20wt.% sulfuric acid aqueous solution as electrolyte, and the current density is 1-2A/dm 2 The anodic oxidation film aluminum material is obtained at the temperature of 20-30 ℃ for 30-100min, the obtained anodic oxidation film aluminum material is reamed by using 5-7wt.% phosphoric acid at the temperature of 35 ℃ for 40-50min, and is vacuum-dried, wherein the thickness of the oxidation film is 10-20 microns, and the aperture is 0.5-0.7 mu m.
4. The graphene oxide-carbon rod composite material according to claim 1, wherein the preparation method of the pitch resin polymer in the step (2) comprises the following steps: filling benzaldehyde, anthracene and concentrated sulfuric acid into a three-mouth bottle, evacuating by using nitrogen, obtaining a black asphalt resin product under the condition of continuous stirring at 135 ℃, repeatedly washing by using propanol, filtering and drying to obtain a pale yellow powder solid, dissolving the pale yellow powder into tetrahydrofuran, stirring for 30min, adding the reamed oxide film aluminum product obtained in the step (1), continuing stirring, carrying out auxiliary vacuumizing to 10-20Pa, filling for 12-24h, and then carrying out rotary evaporation to obtain the pale yellow oxide film aluminum product, and carbonizing for 4h at 800 ℃ under the nitrogen atmosphere.
5. A graphene oxide-carbon rod composite material according to claim 1 wherein the mechanical polishing is a polishing wheel polishing for removing non-porous carbon material from the anodic oxide film porous layer.
6. A graphene oxide-carbon rod composite material according to claim 1, wherein the strong acid is 15wt.% H 2 SO 4 And 10wt.% HNO 3 The volume ratio is VH 2 SO 4 :VHNO 3 =1:1, and reflux-treated at 100 ℃ for 3h under stirring.
7. The method for preparing the graphene oxide-carbon rod composite material according to claim 1, which is characterized by comprising the following steps:
(1) Preparing 20-25wt.% graphene oxide aqueous solution by a hummer method;
(2) Preparing 10-15wt.% of an aqueous carbon rod solution;
(3) Introducing the carbon rod aqueous solution in the step (2) into the graphene oxide aqueous solution in the step (1), and performing auxiliary ultrasonic and stirring treatment;
(4) And (5) performing freeze drying treatment to obtain the graphene oxide-carbon rod composite material.
8. The method for preparing the graphene oxide-carbon rod composite material according to claim 7, wherein the ultrasonic parameters are as follows: the ultrasonic frequency is 40-50 kHz, and the ultrasonic time is 1-3h under the condition that the ultrasonic power is 500-600W.
9. The method for preparing the graphene oxide-carbon rod composite material according to claim 7, wherein the stirring parameters are as follows: the stirring speed is 180-500 r/min, the stirring time is 1-3h, and the stirring temperature is 30-50 ℃.
10. The method for preparing the graphene oxide-carbon rod composite material according to claim 7, wherein the drying pressure of vacuum freeze drying is 5-10Pa, the cold trap temperature is-20 to-60 ℃, and the time is 24-48h.
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| WO2017116657A1 (en) * | 2015-12-28 | 2017-07-06 | Nanotek Instruments, Inc. | Graphene-Carbon Hybrid Foam |
| CN106848248A (en) * | 2017-03-08 | 2017-06-13 | 哈尔滨工业大学 | The preparation method of graphene-supported hollow carbon sphere composite |
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