CN112169845A - Preparation method of composite carbon catalytic material - Google Patents
Preparation method of composite carbon catalytic material Download PDFInfo
- Publication number
- CN112169845A CN112169845A CN202011235071.1A CN202011235071A CN112169845A CN 112169845 A CN112169845 A CN 112169845A CN 202011235071 A CN202011235071 A CN 202011235071A CN 112169845 A CN112169845 A CN 112169845A
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- carbon
- stirring
- graphene
- carbon rod
- oxide film
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- 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
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
The invention provides a preparation method of a composite carbon catalytic material, wherein a carbon rod is used as an intercalation agent of graphene, can effectively separate the 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 PROX gas-solid phase catalytic reaction under a hydrogen-rich condition.
Description
Technical Field
The invention relates to a preparation method of a composite carbon catalytic material, belongs to the field of preparation of carbon materials by using templates, and particularly relates to the field of preparation of nano carbon materials by using an electrochemical anodic oxidation method.
Technical Field
As a novel efficient, clean and renewable resource, hydrogen energy is mainly prepared by hydrocarbon reforming and water gas shift reaction. Due to the thermodynamic limitations of the process, the hydrogen rich gas produced contains 0.5-2 vol.% CO overall. Since the electrode material of a fuel cell is generally Pt, CO in the reformed gas not only poisons the Pt electrode but also easily adsorbs to the surface of the catalyst to further inhibit the catalytic oxidation of the fuel, the CO content in the hydrogen-rich gas must be limited to 100ppm or less. The preferential oxidation of carbon monoxide is one of the most effective methods for purifying CO in hydrogen-rich gas at present.
The reported preferential oxidation catalysts for high-efficiency CO mainly include noble metal (Pt, Ru, Rh, Pd, Ir, etc.) catalysts, oxide catalysts (CuO-CeO2), and gold-based catalysts. Among them, platinum-based bimetallic catalysts have been widely paid attention to with excellent activity, high selectivity and stability, and for example, Pt-Co/SiO2, Pt-Ni/Al2O3, Pt-La/mordenite, Pt-Fe/CeO2, and Pt-alkali metal/Al 2O3 bimetallic catalysts all show 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. In addition, Chin finds that the Pt-Ru/SiO2 catalyst has extremely high activity and stability in a low-temperature stage, Schubert also reports that the Pt-Sn/Al2O3 catalyst can obviously improve the stability of Pt and improve the high-temperature selectivity of the catalyst in the preferential oxidation process of CO.
At present, a series of carbon-based composite materials, such as activated carbon, graphite fiber, carbon nanotube and graphene, are important to research because they have excellent mechanical properties, thermal conductivity and chemical properties as excellent carriers. Kumari adopts a vapor deposition method to grow multi-wall carbon nanotubes on the surface of alumina, and then adopts a discharge plasma sintering method to prepare various CNT-Al2O3 compounds. Worsley prepared a series of SWNT/oxide (SiO2, SnO2, TiO2) monolithic composites by depositing the oxide on the surface of a carbon nanotube carbon aerogel. And graphene-based catalysts are widely used in the field of catalysis, but focus on some liquid-phase catalytic reactions. The palladium (Pd) nanoparticles are uniformly dispersed on the surface of the single-layer graphene by Truong-Huu, and the single-layer graphene is applied to a liquid-phase selective C ═ C hydrogenation reaction. The high-efficiency hydrogenation activity is mainly used for the 2D graphene structure with a single-layer uniformly dispersed structure in a liquid phase, and the structure has extremely high surface area, interface and easy edge adsorption. However, the problem of sizing of the carbon nanotube-based catalyst (for example, the carbon nanotubes are easy to fall off and peel off on a carrier; active particles are wrapped between large graphene layers and cannot contact with a gas phase) is difficult to solve due to the graphene, and the application of the novel carbon material in gas-solid phase catalytic reaction, such as CO-PROX reaction, is severely limited.
Based on the above, it can be clearly seen that when graphene is used as a catalyst carrier in the prior art, the graphene is mainly used as a doping agent, namely the graphene modified silicon oxide, aluminum oxide or titanium oxide is used, the graphene is rarely directly used as a gas-solid phase catalyst carrier, the main reason is that the graphene with a single layer or less than 100 layers is difficult to obtain due to the defect of hummer, even if single-layer graphene is obtained, the single-layer graphene can be only present in a small amount and cannot be obtained in a large amount, when the graphene is dried, stacking and agglomeration of graphene sheet layers occur more, when the graphene is used as a catalyst carrier, an active component is clamped between the graphene sheet layers, so that gas cannot contact with the active component in the graphene, therefore, in the prior art, graphene solid is rarely directly used as a carrier, as in the graduation paper: the novel carbon material composite catalyst is used for preferential oxidation of CO and complete oxidation reaction of CO under hydrogen atmosphere, which is recorded in the prior art, graphene is prepared by hummer, and then an active component Pt is loaded on the graphene for complete oxidation reaction of CO (the raw material gas composition is 1vol.% CO, 10vol.% O2 and 89vol.% N2), and 100-oThe activity of C is only 30%, but the reactivity is extremely low under such excellent reaction conditions, and under the existing harsh conditions of preferential oxidation of 1vol.% CO, 1vol.% O2, 50vol.% H2 and 48vol.% N2, or under the existing equilibrium gas conditions of practical industrial use of 1vol.% CO, 1vol.% O2,12.5 vol.% CO2,15 vol.% H2O,50 vol.% H2 and N2, the catalytic reaction is feasibly lower than 10%, that is, the problem of agglomeration of graphene materials or interlayer agglomeration severely limits the application of the agglomerated graphene in the field of catalyst carriers.
Disclosure of Invention
Based on the limitation of graphene in practical use caused by the agglomeration problem in the prior art, the invention provides a preparation method of a composite carbon catalytic material, wherein the composite carbon catalytic material takes graphene oxide and a carbon rod composite carbon material as a catalyst carrier and Ru as an active component, the carbon rod is intercalated between graphene oxide sheet layers, the length of the carbon rod is 10-20 mu m, the diameter of the carbon rod is 0.5-0.7 mu m, and the oxidized carbon rod is intercalated between graphene oxide sheet layersThe specific surface area of the graphene-carbon rod composite material is 289g-357m2The mesoporous aperture is 5-10 nm.
The preparation method of the graphene oxide-carbon rod composite material comprises the following steps:
(1) preparing 20-25wt.% graphene oxide aqueous solution by hummer method, adding 25ml concentrated sulfuric acid into dry four-neck flask, and cooling to 0-2 with ice bathoC, adding 0.5g of natural crystalline flake graphite and 0.5g of NaNO into the mixture while stirring3And slowly adding 3g KMnO4Particles, this stage is a low temperature reaction. Then placing the flask in a constant temperature water bath at about 35 ℃, and continuing stirring for 4 hours when the temperature of the reaction liquid rises to about 35 ℃, thus finishing the medium temperature reaction. 46ml of deionized water were then slowly added to the solution at 98oStirring for 15min under C, reacting at high temperature, adding 140ml deionized water and 3ml H2O2(30wt.%) reaction for 40 min. And finally, washing the graphite oxide solution to be neutral for multiple times by using deionized water.
(2) Preparation of 10-15wt.% carbon rod aqueous 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 in the oxide film pore canal for multiple times by taking the porous oxide film as a hard template and the pitch resin polymer as the carbon source;
(c) mechanically polishing the material obtained in the step (2);
(d) corroding the material obtained in the step (3) by using strong acid, and removing the hard template;
(e) washing, drying and dissolving to obtain a carbon rod aqueous solution;
(3) introducing the carbon rod aqueous solution obtained in the step (2) into the graphene oxide aqueous solution obtained in the step (1) to assist ultrasonic stirring treatment;
(4) carrying out first vacuum freeze drying treatment to obtain a graphene oxide-carbon rod composite material;
(5) impregnating Ru (NO) by an isovolumetric impregnation method3)3 .xH2O, the dipping time is 12 h;
(6) and (4) performing secondary vacuum freeze drying to obtain the Ru/graphene-carbon rod composite carbon catalytic material.
Further, the loading amount of Ru in the Ru/graphene-carbon rod composite carbon catalytic material is 3-7 wt.%.
Further, the substrate is pretreated: degreasing-washing-pickling-washing-alkaline etching-washing-brightening-washing, wherein the degreasing solution: 45g/L sodium bicarbonate, 45g/L sodium carbonate, 40 deg.CoC; acid washing solution: hydrofluoric acid 0.02g/L, sulfuric acid 4g/L, surfactant 1g/L, temperature room temperature, alkaline etching solution: 45g/L of sodium hydroxide, 1g/L of sodium gluconate and 40 ℃ of temperatureoC, the time is 2-3 min; brightening liquid: 350g/L nitric acid solution for 2-3 min.
Further, the process of step (1) is as follows: aluminum or aluminum alloy is used as a base material, an inert lead material is used as a cathode, 10-20wt.% sulfuric acid aqueous solution is used as electrolyte, and the current density is 1-2A/dm2The time is 30-100min, and the temperature is 20-30oC, obtaining an anodized aluminum material, and putting the obtained anodized aluminum material at 35 DEGoAnd C, expanding the pores by using 5-7wt.% phosphoric acid for 40-50min, and performing vacuum drying, wherein the thickness of the oxide film is 10-20 microns, and the pore diameter is 0.5-0.7 mu m.
Further, the preparation method of the pitch resin polymer in the step (2) is as follows: placing benzaldehyde, anthracene and concentrated sulfuric acid into a three-neck bottle, evacuating with nitrogen, and introducing at 135 deg.CoC, obtaining a black asphalt resin product under the condition of continuous stirring, repeatedly washing with propanol, filtering and drying to obtain a light yellow powder solid, dissolving the light yellow powder in tetrahydrofuran, stirring for 30min, adding the hole-expanded aluminum oxide film obtained in the step (1), continuously stirring, performing auxiliary vacuum pumping to 10-20Pa, filling for 12-24h, performing rotary evaporation to obtain the light yellow aluminum oxide film, further reacting with nitrogen atmosphere to obtain 800 parts of light yellow aluminum oxide filmoAnd C, carbonizing for 4 hours.
Further, the mechanical polishing is polishing wheel grinding and is used for removing non-porous carbon materials on the porous layer of the anodic oxide film.
Further, the strong acid is 15wt.% of H2SO4And 10wt.% HNO3Body ofProduct ratio is VH2SO4:VHNO31:1, under stirring at 100oC, refluxing for 3 h.
Further, the ultrasound parameters are: the ultrasonic frequency is 40-50 KHz, the ultrasonic power is 500-600W, and the ultrasonic time is 1-3 h.
Further, 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 30-50oC。
Furthermore, the drying pressure of the vacuum freeze drying is 5-10Pa, the temperature of a cold well is-20 to-60 ℃, and the time is 24-48 h.
Regarding the preparation method:
(1) preparing graphene oxide by hummer: adding 25ml of concentrated sulfuric acid into a dry four-neck flask, and cooling to 0-2% with ice bathoC, adding 0.5g of natural crystalline flake graphite and 0.5g of NaNO into the mixture while stirring3And slowly adding 3g KMnO4Particles, this stage is a low temperature reaction. Then placing the flask in a constant temperature water bath at about 35 ℃, and continuing stirring for 4 hours when the temperature of the reaction liquid rises to about 35 ℃, thus finishing the medium temperature reaction. 46ml of deionized water were then slowly added to the solution at 98oStirring for 15min under C, reacting at high temperature, adding 140ml deionized water and 3ml H2O2(30wt.%) reaction for 40 min. Finally, the graphite oxide solution is washed to be neutral for many times by using deionized water, which is a typical low-temperature-medium-high-temperature hummer method, the invention does not exclude other methods for preparing graphene oxide in the prior art, and only an exemplary illustration is given here, and the obtained graphene oxide lamellar is thin, as shown in fig. 8.
(2) For the preparation of 10-15wt.% carbon rod aqueous solutions:
as shown in the attached figure 1, the base material is pretreated, anodized to prepare a hard template, filled, polished and corroded to finally obtain the carbon nano-rod.
(a) Regarding the pretreatment: no matter what kind of surface treatment process, to obtain good effect, clean surface is the first condition, this application hopes to obtain the anodic oxide film with uniform nanometer pore canal and uniform thickness, therefore the pretreatment is the basis for obtaining the uniform oxide film in each direction, the base material of the invention is pretreated: degreasing, washing with water, pickling, washing with water, alkaline etching, washing with water, brightening and washing with water.
Wherein the degreasing solution: 45g/L sodium bicarbonate, 45g/L sodium carbonate, 40 deg.CoAnd C, before the surface of the workpiece is treated, oil stains on the surface must be removed firstly to ensure the bonding strength of the conversion coating and the matrix metal, ensure the chemical reaction of the conversion coating to be smoothly carried out and obtain the conversion coating with qualified quality.
Acid washing solution: 0.02g/L of hydrofluoric acid, 4g/L of sulfuric acid, 1g/L of surfactant, room temperature, and acid cleaning to remove dirt and oxide on the surface without hydrogen embrittlement, wherein the acid degreasing mechanism of the aluminum alloy is as follows: oxides on the surface of the aluminum are dissolved to loosen the oil stains, and the oil stains are separated from the metal surface by utilizing the action of water flow.
Alkaline etching solution: 45g/L of sodium hydroxide, 1g/L of sodium gluconate and 40 ℃ of temperatureoC, the time is 2-3min, the aluminum alloy workpiece can not be subjected to conversion film treatment after a degreasing process, the surface generally has defects of a natural oxide film, processing stripes and the like, and the natural oxide film needs to be removed by corrosion treatment to activate the surface. The alkaline etching is the most common etching process, the main component is NaOH solution, the cost is low, the maintenance and the management are easy, and the alkaline etching is used for removing the oxide film which can not be removed by acid cleaning.
Brightening liquid: 350g/L nitric acid solution for 2-3 min. The surface of the workpiece corroded by acid and alkali is often dark, because the surface of the aluminum alloy containing high copper content has copper oxide, and black hanging ash is formed. In order to brighten the surface of the workpiece, the polishing treatment is usually performed in a nitric acid solution.
(b) Regarding anodic oxidation: adopting 10-20wt.% sulfuric acid aqueous solution as electrolyte, and having current density of 1-2A/dm2The time is 30-100min, and the temperature is 20-30oC, the thickness of the obtained anodic oxide film aluminum material is 10-20 microns, the pore diameter is concentrated below 500nm and is small, as shown in figure 5, the pore diameter is not beneficial to subsequent filling of carbon precursors, and therefore the obtained anodic oxide film aluminum material is 35 DEGoAnd C, expanding the pores by using 5-7wt.% phosphoric acid for 40-50min, and performing vacuum drying to complete the pore expansion of the anode oxide film pore canal, which is favorable forIn the process of filling and reaming the carbon precursor, the thickness is not obviously reduced or is not obviously reduced, the pore diameter is expanded to 0.5-0.7 mu m, as shown in figure 6, the hard template is an anodic oxide film pore path hard template for reaming for 20min, as shown in figure 7, the hard template is an anodic oxide film hard template for reaming for 45 min.
(c) Regarding the preparation of the precursor: the carbon precursor is selected according to the principle that the molecular size is suitable for entering the pore channel of the anodic oxide film template, the compatibility (wettability and hydrophilicity) with the pore wall is good, and the polymer substance separated or further polymerized in the pore has higher carbonization yield and the like. At present, carbon precursors mainly comprise sucrose, xylose, glucose, furfuryl alcohol resin, phenolic resin, mesophase pitch, anthracene, phenanthrene, divinylbenzene and some organic solvents such as ethanol, methanol, toluene and the like. There are also a number of ways to introduce different precursors into the channels of the hard template, the most common being mainly solution impregnation, the type of carbon precursor also having a large influence on the structure of the final carbon material. The furfuryl alcohol is used as a carbon precursor, and mesoporous carbon with good order can be easily prepared; when the mesophase pitch is used as the carbon precursor, the microporosity of the material can be obviously reduced, and the carbon yield is high; in addition, the type of the carbon precursor has a very important influence on the graphitization degree of the finally obtained carbon material, and the precursor (such as phenolic resin) with a loose molecular structure and high oxygen content can obtain a hard carbon material containing a large amount of micropores and high oxygen content after carbonization, and the hard carbon material is difficult to graphitize. The precursor (such as anthracene) containing no oxygen and having a condensed ring structure can be carbonized to obtain a mesoporous carbon material with higher graphitization degree.
The preparation method comprises the following steps: placing benzaldehyde, anthracene and concentrated sulfuric acid into a three-neck bottle, evacuating with nitrogen, and introducing at 135 deg.CoC, obtaining a black asphalt resin product under the condition of continuous stirring, repeatedly washing with propanol, filtering and drying to obtain a light yellow powder solid, dissolving the light yellow powder in tetrahydrofuran, stirring for 30min, adding the hole-expanded aluminum oxide film obtained in the step (1), continuously stirring, performing auxiliary vacuum pumping, filling for 12-24h, and then performing auxiliary vacuum pumpingRotary evaporating to obtain yellowish aluminum oxide film, and reacting with nitrogen gas in 800 deg.CoAnd C, carbonizing for 4 hours.
In the process, attention needs to be paid to (a) temperature and moisture in the filling process, so that the water-based hole sealing phenomenon of an anodic oxide film is avoided, and the filling of the carbon precursor liquid is obviously reduced due to the sealing of holes; (b) stirring and vacuumizing are necessary means, and due to the viscosity of the asphalt polymer and the difficulty in the filling process, the asphalt polymer must be stirred constantly and vacuumized, and the auxiliary carbon precursor enters a pore channel and then is subjected to evaporation, drying and carbonization processes; (c) the number of filling times is determined as needed, and the more the better, the more the filling is sufficient.
In addition, the quality of the hard template of the anodic oxidation porous membrane, the filling amount of the carbon precursor and the carbonization process all influence the mesostructure of the carbon nano-rod to a great extent. Of particular importance is the choice of carbon precursor. The carbon precursor molecules can interact with the template molecules to form an ordered mesostructure. Secondly, precursor molecules must be capable of being crosslinked with each other to form a thermosetting polymer network, and deformation caused by skeleton shrinkage in the process of high-temperature carbonization and template removal can be guaranteed to be resisted in the template removal engineering through the formation of the polymer network. In addition, different carbon precursors can undergo different carbonization processes, and further, the mesostructure of the carbon rod can be influenced, and the microstructure such as graphitization degree can also be influenced. Therefore, the carbon precursor molecule is required to have the characteristics of proper size, good thermal stability, abundant warp groups, high residual carbon content of the polymer, and the like.
(d) Regarding the grinding: mechanical polishing is a key step for controlling morphology, when the carbon precursor is excessively filled as shown in figure 1, carbon materials are attached to the surface of the anodic oxide film, polishing is needed to remove the non-pore carbon materials on the porous layer of the anodic oxide film, one end of the finally obtained carbon rod is a semi-arc section at the position of the barrier layer of the anodic oxide film, and the other end of the carbon rod is a mechanically polished flat line end, as shown in figure 2, one end of the carbon rod is arc-shaped, and the other end of the carbon rod is a flat line end.
(e) With respect to corrosion, forIn terms of anodized aluminum, the base materials are aluminum oxide and aluminum materials, and due to the amphoteric property of aluminum materials, acidic solution or alkaline solution can be used for corrosion, but the alkaline corrosion is abandoned in the application, because the invention needs to introduce a large amount of hydrophilic free radicals such as hydroxyl, oxygen and the like on the surface of a carbon material besides removing aluminum material templates, and the alkaline corrosion is not enough, so that 15wt.% of H is used as strong acid2SO4And 10wt.% HNO3Volume ratio of VH2SO4:VHNO31:1, under stirring at 100oC, refluxing for 3h, introducing hydroxyl through strong acid corrosion and refluxing, 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) shown in an attached figure 2, the carbon rod disclosed by the invention is uniformly dispersed and low in polymerization, and the application field of the carbon rod is remarkably widened due to the existence of the dispersed state.
As shown in the attached FIG. 3 and FIG. 4, the top view and the side view of the structured carbon rod material obtained after the structured carbon rod material is directly corroded without being ground.
(3) Regarding the mixing: directly mixing 20-25wt.% of graphene oxide aqueous solution prepared by a hummer method and 10-15wt.% of carbon rod aqueous solution prepared by a template method, wherein the addition of the two solutions has no obvious difference, and the key point is ultrasonic and stirring treatment; by adding ultrasound and stirring: the ultrasonic frequency is 40-50 KHz, the ultrasonic power is 500-600W, and the ultrasonic time is 1-3 h; the stirring speed is 180-500 r/min, the stirring time is 1-3h, and the stirring temperature is 30-50oAnd C, the graphene sheet layers can be further dispersed remarkably, and graphite carbon rods can be favorably dispersed among the graphene sheet layers, as shown in a TEM (transmission electron microscope) shown in figure 9, black carbon rods exist between two pieces of graphene oxide, the carbon rods can be used as an intercalator to effectively disperse the graphene sheet layers, as shown in figure 10, part of the carbon rods obviously jack up the graphene sheet layers, and the graphene sheet layers are effectively dispersed.
(4) For vacuum freeze drying: the drying technology is necessary and has irreplaceability, the actual state of the carbon material in the aqueous solution can be remarkably maintained due to vacuum freeze drying, so that the drying technology can effectively avoid the reagglomeration of the graphene, if technologies such as air-blast drying, spin drying and evaporation drying are used, the carbon composite material is found to be attached to the surface of a drying vessel in a sticky manner, and the freeze drying is used, the carbon composite material is flocculent in the drying vessel and can be directly poured out of the drying vessel, 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 temperature of a cold well is-20-60 ℃, and the time is 24-48 h.
(5) As the active component, any of the active noble metals in the prior art may be used, such as Pt, Ru and Rh, and Ru is preferable here, and further, the impregnation method is an equivalent-volume impregnation method.
(6) For the second vacuum freeze drying, the preparation method for standby of the invention is as follows:
(1) preparing 20-25wt.% graphene oxide aqueous solution by a hummer method;
(2) preparing 10-15wt.% carbon rod aqueous solution;
(3) introducing the carbon rod aqueous solution obtained in the step (2) into the graphene oxide aqueous solution obtained in the step (1), performing auxiliary ultrasonic treatment and stirring treatment, wherein the ultrasonic time is 1-3h and the stirring time is 1-3h, the ultrasonic time is less than the stirring time, such as ultrasonic time of 1h, stirring for 1.5h, stopping ultrasonic treatment, and adding a proper amount of Ru (NO) into the phase solution in the stirring process3)3 .xH2O, over-volume impregnation, impregnation for 12h, and vacuum freeze-drying to obtain a graphene oxide-carbon rod composite material, wherein only one-time drying is adopted, because the secondary drying is easy to cause the compounding of graphene layers, as known by the technical personnel in the field, the dry graphene oxide can generate a stacking layer re-adhesion phenomenon, the specific surface area of the carrier is reduced, but the over-volume impregnation is serious in the waste of a solution of noble metal, the content of an active component in the finally obtained catalyst is greatly reduced, and the attempt is not made, so the comprehensive judgment is that the secondary freeze-drying is preferred, the active component ruthenium is obtained by an equal-volume impregnation method and is highly dispersed on the surface of the catalyst carrier, and as shown in the attached drawing, the active component ruthenium is13, highly dispersed Ru particles can be seen in the process of SEM image of active component in Ru/graphene-carbon rod composite carbon catalytic material, and carbon rod material can be seen in rare.
The scheme of the invention has the following beneficial effects:
(1) the carbon rods prepared by the template method are almost identical in size, size and shape.
(2) The nanometer carbon rods are highly dispersed and are uniform in all directions.
(3) The carbon rod can be used for a graphene dispersion intercalation agent, can be used as a raw material of a carbon electrode, can be used as a catalyst carrier, and has a wide application field.
(4) The existence of the carbon rod intercalation agent can obviously improve the specific surface area of the graphene material and provide a reaction site for gas-solid phase catalytic reaction.
(5) For PROX reaction, the active components are highly dispersed on the surface of the catalyst, so that the catalytic activity and the selectivity are high.
Drawings
FIG. 1 is a schematic view of a method for preparing a carbon nanorod according to the present invention.
FIG. 2 is a TEM image of the carbon nanorods of the invention under water-ethanol conditions.
Fig. 3 is a SEM top view of the nano rod-shaped carbon material without being polished according to the present invention.
Fig. 4 is a side view of the nano rod-shaped carbon material without being ground according to the present invention.
Fig. 5 is an SEM image of the non-reamed channels of the anodized film of the present invention.
FIG. 6 is an SEM image of the anode oxide film pore canals reamed for 20 min.
FIG. 7 is an SEM image of the anodic oxide film pore canals reamed for 45 min.
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 the graphene-carbon rod composite carbon support of the present invention.
Fig. 10 is an SEM image of the graphene-carbon rod composite carbon support of the present invention.
FIG. 11 shows a graphene-carbon rod according to the present inventionN of composite carbon carrier2Physical adsorption desorption isotherms.
Fig. 12 is a BJH pore size distribution line of the graphene-carbon rod composite carbon carrier of the present invention.
Fig. 13 is an SEM image of active components in the Ru/graphene-carbon rod composite carbon catalytic material of the present invention.
Detailed Description
Example 1
A preparation method of a composite carbon catalytic material comprises the following processing steps:
(1) a 20wt.% aqueous solution of graphene oxide was prepared by hummer method.
(2) Preparation of a 10wt.% carbon rod aqueous solution:
(a) pretreatment: sequentially carrying out degreasing, washing, pickling, washing, alkaline etching, washing, brightening and washing on the aluminum material, wherein the degreasing solution: 45g/L sodium bicarbonate, 45g/L sodium carbonate, 40 deg.CoC; acid washing solution: hydrofluoric acid 0.02g/L, sulfuric acid 4g/L, surfactant 1g/L, temperature room temperature, alkaline etching solution: 45g/L of sodium hydroxide, 1g/L of sodium gluconate and 40 ℃ of temperatureoC, the time is 2 min; brightening liquid: 350g/L nitric acid solution for 2 min.
(b) Taking an aluminum material as a base material, and forming a porous oxide film on the surface of the aluminum material by an electrochemical method, wherein the pretreated aluminum material is taken as an anode, an inert lead material is taken as a cathode, a 10wt.% sulfuric acid aqueous solution is taken as an electrolyte, and the current density is 1A/dm2Time 30min, temperature 20oC, obtaining an anodized aluminum material, and putting the obtained anodized aluminum material at 35 DEGoAnd C, expanding the pores by using 5wt.% phosphoric acid for 40min, and performing vacuum drying.
(c) And repeatedly filling the carbon source in the pore canal of the oxide film for many times by taking the porous oxide film as a hard template and the pitch resin polymer as the carbon source, wherein the preparation method of the pitch resin polymer comprises the following steps: placing benzaldehyde, anthracene and concentrated sulfuric acid into a three-neck bottle, evacuating with nitrogen, and introducing at 135 deg.CoC, obtaining a black asphalt resin product under the condition of continuous stirring, repeatedly washing, filtering and drying by using propanol to obtain a light yellow powder solid, and dissolving the light yellow powder in tetrahydrofuranStirring for 30min, adding the chambered oxide film aluminum material obtained in the step (1), continuously stirring, performing auxiliary vacuum pumping until the vacuum degree is 10Pa, filling for 12h, performing rotary evaporation to obtain a light yellow oxide film aluminum material, further reacting with nitrogen atmosphere, and performing 800oCarbonizing for 4 hours under 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 non-porous carbon materials on the porous layer of the anodic oxide film.
(e) And (3) corroding the material obtained in the step (3) by using strong acid, and removing the hard template: the strong acid is 15wt.% of H2SO4And 10wt.% HNO3Volume ratio of VH2SO4:VHNO31:1, under stirring at 100oC, refluxing for 3 h.
(f) Washing, drying and dissolving to obtain a carbon rod aqueous solution: the washing is carried out by washing for many times with deionized water until the solution is neutral, filtering and drying to 60oAnd C, blowing and drying for 12 hours.
(3) Introducing the carbon rod aqueous solution obtained in the step (2) into the graphene oxide aqueous solution obtained in the step (1), and performing auxiliary ultrasonic stirring treatment: ultrasonic parameters: the ultrasonic frequency is 40KHz, the ultrasonic power is 500W, the ultrasonic time is 1h, and the stirring parameters are as follows: the stirring speed is 180r/min, the stirring time is 1h, and the stirring temperature is 30oC。
(4) Carrying out primary freeze drying treatment to obtain the graphene oxide-carbon rod composite material, wherein the drying pressure of vacuum freeze drying is 5-10Pa, the temperature of a cold well is-20 to-60 ℃, and the time is 24 hours to obtain the graphene oxide-carbon rod composite material;
(5) impregnating Ru (NO) by an isovolumetric impregnation method3)3 .xH2O, immersion time 12h, Ru loading 3 wt.%;
(6) and (3) performing secondary vacuum freeze drying under the condition consistent with that of the primary vacuum drying to obtain the 3wt.% Ru/graphene-carbon rod composite carbon catalytic material.
Example 2
A preparation method of a graphene oxide-carbon rod composite material comprises the following processing steps:
(1) a 22.5wt.% aqueous solution of graphene oxide was prepared by the hummer method.
(2) Preparation of 12.5wt.% carbon rod aqueous solution:
(a) pretreatment: sequentially carrying out degreasing, washing, pickling, washing, alkaline etching, washing, brightening and washing on the aluminum material, wherein the degreasing solution: 45g/L sodium bicarbonate, 45g/L sodium carbonate, 40 deg.CoC; acid washing solution: hydrofluoric acid 0.02g/L, sulfuric acid 4g/L, surfactant 1g/L, temperature room temperature, alkaline etching solution: 45g/L of sodium hydroxide, 1g/L of sodium gluconate and 40 ℃ of temperatureoC, the time is 2.5 min; brightening liquid: 350g/L nitric acid solution for 2.5 min.
(b) Taking an aluminum material as a base material, and forming a porous oxide film on the surface of the aluminum material by an electrochemical method, wherein the pretreated aluminum material is taken as an anode, an inert lead material is taken as a cathode, a 15wt.% sulfuric acid aqueous solution is taken as an electrolyte, and the current density is 1.5A/dm2The time is 30-100min, and the temperature is 25oC, obtaining an anodized aluminum material, and putting the obtained anodized aluminum material at 35 DEGoUnder C, 6wt.% phosphoric acid is used for reaming for 45min, and vacuum drying is carried out.
(c) And repeatedly filling the carbon source in the pore canal of the oxide film for many times by taking the porous oxide film as a hard template and the pitch resin polymer as the carbon source, wherein the preparation method of the pitch resin polymer comprises the following steps: placing benzaldehyde, anthracene and concentrated sulfuric acid into a three-neck bottle, evacuating with nitrogen, and introducing at 135 deg.CoC, obtaining a black asphalt resin product under the condition of continuous stirring, repeatedly washing with propanol, filtering and drying to obtain a light yellow powder solid, dissolving the light yellow powder in tetrahydrofuran, stirring for 30min, adding the hole-expanded aluminum oxide film obtained in the step (1), continuously stirring, performing auxiliary vacuum pumping until the vacuum degree is 10-20Pa, filling for 18h, performing rotary evaporation to obtain the light yellow aluminum oxide film, and further performing 800-step nitrogen atmosphereoCarbonizing for 4 hours under 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 non-porous carbon materials on the porous layer of the anodic oxide film.
(e) And (3) corroding the material obtained in the step (3) by using strong acid, and removing the hard template: the strong acid is 15wt.% of H2SO4And 10wt.% HNO3Volume ratio of VH2SO4:VHNO31:1, under stirring at 100oC, refluxing for 3 h.
(f) Washing, drying and dissolving to obtain a carbon rod aqueous solution: the washing is carried out by washing for many times with deionized water until the solution is neutral, filtering and drying to 60oAnd C, blowing and drying for 12 hours.
(3) Introducing the carbon rod aqueous solution obtained in the step (2) into the graphene oxide aqueous solution obtained in the step (1), and performing auxiliary ultrasonic stirring treatment: ultrasonic parameters: the ultrasonic frequency is 45KHz, the ultrasonic power is 550W, the ultrasonic time is 2h, and the stirring parameters are as follows: the stirring speed is 300r/min, the stirring time is 2h, and the stirring temperature is 40oC。
(4) Carrying out primary freeze drying treatment to obtain the graphene oxide-carbon rod composite material, wherein the drying pressure of vacuum freeze drying is 5-10Pa, the temperature of a cold well is-20 to-60 ℃, and the time is 38h to obtain the graphene oxide-carbon rod composite material;
(5) impregnating Ru (NO) by an isovolumetric impregnation method3)3 .xH2O, immersion time 12h, Ru loading 5 wt.%;
(6) and (3) performing secondary vacuum freeze drying under the condition consistent with that of the primary vacuum drying to obtain the 5wt.% Ru/graphene-carbon rod composite carbon catalytic material.
Example 3
A preparation method of a graphene oxide-carbon rod composite material comprises the following processing steps:
(1) a 25wt.% aqueous solution of graphene oxide was prepared by hummer method.
(2) Preparation of a 15wt.% carbon rod aqueous solution:
(a) pretreatment: sequentially carrying out degreasing, washing, pickling, washing, alkaline etching, washing, brightening and washing on the aluminum material, wherein the degreasing solution: 45g/L sodium bicarbonate, 45g/L sodium carbonate, 40 deg.CoC; acid washing solution: hydrofluoric acid 0.02g/L, sulfuric acid 4g/L, surface activity1g/L of agent, room temperature, alkaline etching solution: 45g/L of sodium hydroxide, 1g/L of sodium gluconate and 40 ℃ of temperatureoC, the time is 2-3 min; brightening liquid: 350g/L nitric acid solution for 3 min.
(b) Taking an aluminum material as a base material, and forming a porous oxide film on the surface of the aluminum material by an electrochemical method, wherein the pretreated aluminum material is taken as an anode, an inert lead material is taken as a cathode, a 20wt.% sulfuric acid aqueous solution is taken as an electrolyte, and the current density is 2A/dm2Time 100min, temperature 30oC, obtaining an anodized aluminum material, and putting the obtained anodized aluminum material at 35 DEGoAnd C, expanding the pores by using 7wt.% phosphoric acid for 50min, and performing vacuum drying.
(c) And repeatedly filling the carbon source in the pore canal of the oxide film for many times by taking the porous oxide film as a hard template and the pitch resin polymer as the carbon source, wherein the preparation method of the pitch resin polymer comprises the following steps: placing benzaldehyde, anthracene and concentrated sulfuric acid into a three-neck bottle, evacuating with nitrogen, and introducing at 135 deg.CoC, obtaining a black asphalt resin product under the condition of continuous stirring, repeatedly washing with propanol, filtering and drying to obtain a light yellow powder solid, dissolving the light yellow powder in tetrahydrofuran, stirring for 30min, adding the hole-expanded aluminum oxide film obtained in the step (1), continuously stirring, performing auxiliary vacuum pumping until the vacuum degree is 10-20Pa, filling for 24h, performing rotary evaporation to obtain the light yellow aluminum oxide film, and further performing 800-step nitrogen atmosphereoCarbonizing for 4 hours under 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 non-porous carbon materials on the porous layer of the anodic oxide film.
(e) And (3) corroding the material obtained in the step (3) by using strong acid, and removing the hard template: the strong acid is 15wt.% of H2SO4And 10wt.% HNO3Volume ratio of VH2SO4:VHNO31:1, under stirring at 100oC, refluxing for 3 h.
(f) Washing, drying and dissolving to obtain a carbon rod aqueous solution: the washing is carried out by washing for many times with deionized water until the solution is neutral, filtering and drying to 60oAnd C, blowing and drying for 12 hours.
(3) Introducing the carbon rod aqueous solution obtained in the step (2) into the graphene oxide aqueous solution obtained in the step (1), and performing auxiliary ultrasonic stirring treatment: ultrasonic parameters: the ultrasonic frequency is 50KHz, the ultrasonic power is 600W, the ultrasonic time is 1-3h, and the stirring parameters are as follows: the stirring speed is 500r/min, the stirring time is 3h, and the stirring temperature is 50oC。
(4) Carrying out primary freeze drying treatment to obtain the graphene oxide-carbon rod composite material, wherein the drying pressure of vacuum freeze drying is 5-10Pa, the temperature of a cold well is-20 to-60 ℃, and the time is 48h to obtain the graphene oxide-carbon rod composite material;
(5) impregnating Ru (NO) by an isovolumetric impregnation method3)3 .xH2O, immersion time 12h, Ru loading 7 wt.%;
(6) and (3) performing secondary vacuum freeze drying under the condition consistent with that of the primary vacuum drying to obtain the 7wt.% Ru/graphene-carbon rod composite carbon catalytic material.
Comparative example 1
Adding 25ml of concentrated sulfuric acid into a dry four-neck flask, and cooling to 0-2% with ice bathoC, adding 0.5g of natural crystalline flake graphite and 0.5g of NaNO into the mixture while stirring3And slowly adding 3g KMnO4Particles, this stage is a low temperature reaction. Then placing the flask in a constant temperature water bath at about 35 ℃, and continuing stirring for 4 hours when the temperature of the reaction liquid rises to about 35 ℃, thus finishing the medium temperature reaction. 46ml of deionized water were then slowly added to the solution at 98oStirring for 15min under C, reacting at high temperature, adding 140ml deionized water and 3ml H2O2(30wt.%) reacting for 40min, deionizing, washing with acetone for several times to neutrality, drying in 40-50 deg.C blast furnace, and loading active component by equivalent-volume impregnation method to 3 wt.%.
The preparation method of graphene oxide used in the above-mentioned examples 1-3 is exactly the same as that of comparative example 1, and the graphene obtained in example 2 and comparative example 1 is compared, and shown as N in FIG. 112Physical adsorption desorption isotherm, BJH pore size distribution line shown in figure 12, in which the specific surface areaThe pore volume and the mesopore size are summarized as follows.
TABLE 1
The results clearly show that the specific surface area of the graphene oxide can be obviously improved by using the carbon rod as the intercalation agent, and the carbon rod as the intercalation agent effectively props up the graphene, so that the pore diameter is increased, the pore volume is increased, and a necessary reaction site is provided for the graphene oxide-carbon rod composite material as a gas-solid phase catalytic reaction, wherein the carbon rod is obtained from the pore size distribution and pore volume results of the comparative example 1.
The activity test was performed for example 2 and comparative example 1, respectively, at 10vol.% H before reaction2/N2300 in the mixed gasoC reduction pretreatment for 1 hour, the total gas flow rate is 40 ml/min, and the corresponding volume space velocity is 24000ml/gcat.h, feed gas composition of 1vol.% CO, 1vol.% O2,50 vol.% H2And N is2Balancing qi.
Wherein the 5wt.% Ru/graphene-carbon rod composite carbon catalytic material of the embodiment 2 is 100-oC can completely purify CO, and the selectivity is 50 percent and is as low as 1ppm and 200 percentoNo methane alkylation below C, low temperature condition 75oC conversion of 69% and selectivity of 67%, comparative example 1 in the range 50-250oC range has no capability of completely purifying CO and is 150oAnd C, the catalytic activity is optimal and is only 86%, and the high-temperature methanation is serious and the selectivity is low.
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.
Claims (10)
1. The preparation method of the composite carbon catalytic material is characterized in that the composite carbon catalytic material takes graphene oxide and carbon rod composite carbon material as a catalyst carrier, takes Ru as an active component, and the carbon rod is intercalated in the oxidized stoneBetween graphene sheets, wherein the length of the carbon rod is 10-20 μm, the diameter of the carbon rod is 0.5-0.7 μm, and the specific surface area of the graphene oxide and carbon rod composite carbon material carrier is 289g-357m2The 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 in the oxide film pore canal for multiple times by taking the porous oxide film as a hard template and the pitch resin polymer as the carbon source;
(3) mechanically polishing the material obtained in the step (2);
(4) corroding the material obtained in the step (3) by using strong acid, and removing the hard template;
(5) washing, drying and dissolving to obtain the carbon rod aqueous solution.
2. The method of claim 1, further comprising the steps of:
(1) preparing 20-25wt.% graphene oxide aqueous solution by a hummer method;
(2) preparing 10-15wt.% carbon rod aqueous solution;
(3) introducing the carbon rod aqueous solution obtained in the step (2) into the graphene oxide aqueous solution obtained in the step (1), and performing auxiliary ultrasonic and stirring treatment;
(4) carrying out first vacuum freeze drying treatment to obtain a graphene oxide-carbon rod composite material;
(5) impregnating Ru (NO) by an isovolumetric impregnation method3)3 .xH2O, the dipping time is 12 h;
(6) and (4) performing secondary vacuum freeze drying to obtain the Ru/graphene-carbon rod composite carbon catalytic material.
3. The method of claim 2, wherein the Ru loading in the Ru/graphene-carbon rod composite carbon catalytic material is 3-7 wt.%.
4. The method of claim 1, wherein the step (1) comprises the steps of: aluminum or aluminum alloy is used as a base material, an inert lead material is used as a cathode, 10-20wt.% sulfuric acid aqueous solution is used as electrolyte, and the current density is 1-2A/dm2The time is 30-100min, and the temperature is 20-30oC, obtaining an anodized aluminum material, and putting the obtained anodized aluminum material at 35 DEGoAnd C, expanding the pores by using 5-7wt.% phosphoric acid for 40-50min, and performing vacuum drying, wherein the thickness of the oxide film is 10-20 microns, and the pore diameter is 0.5-0.7 mu m.
5. The method of claim 1, wherein the pitch resin polymer in step (2) is prepared by the following steps: placing benzaldehyde, anthracene and concentrated sulfuric acid into a three-neck bottle, evacuating with nitrogen, and introducing at 135 deg.CoC, obtaining a black asphalt resin product under the condition of continuous stirring, repeatedly washing with propanol, filtering and drying to obtain a light yellow powder solid, dissolving the light yellow powder in tetrahydrofuran, stirring for 30min, adding the hole-expanded aluminum oxide film obtained in the step (1), continuously stirring, performing auxiliary vacuum pumping to 10-20Pa, filling for 12-24h, performing rotary evaporation to obtain the light yellow aluminum oxide film, further reacting with nitrogen atmosphere to obtain 800 parts of light yellow aluminum oxide filmoAnd C, carbonizing for 4 hours.
6. The method of claim 1, wherein the mechanical polishing is buff polishing for removing non-porous carbonaceous material on the porous layer of the anodic oxide film.
7. The method of claim 1, wherein the strong acid is 15wt.% H2SO4And 10wt.% HNO3Volume ratio of VH2SO4:VHNO31:1, under stirring at 100oC, refluxing for 3 h.
8. The method of claim 2, wherein the ultrasonic parameters are: the ultrasonic frequency is 40-50 KHz, the ultrasonic power is 500-600W, and the ultrasonic time is 1-3 h.
9. A method of making a composite carbon catalytic material as claimed in claim 2 wherein the stirring parameters are: the stirring speed is 180-500 r/min, the stirring time is 1-3h, and the stirring temperature is 30-50oC。
10. The method for preparing a composite carbon catalytic material as claimed in claim 2, wherein the conditions of the first vacuum freeze-drying and the second vacuum freeze-drying are the same, the pressure is 5-10Pa, the temperature of the cold well is-20 to-60 ℃, and the time is 24-48 h.
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