CN114057190A - Catalyst carrier carbon material for preparing carbon nano tube and preparation method and application thereof - Google Patents
Catalyst carrier carbon material for preparing carbon nano tube and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
-
- B01J35/51—
-
- B01J35/615—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a catalyst carrier carbon material for preparing carbon nanotubes, and a preparation method and application thereof, wherein the preparation method of the carbon material comprises the following steps: providing a conductive particle intercalated graphene oxide dispersion liquid; and granulating the graphene oxide dispersion liquid with the conductive particle intercalation layer to remove the solvent, thereby obtaining the carbon material. The carbon material with excellent loading performance is obtained by a simple and low-cost mode, has excellent comprehensive performance of high specific surface area, difficult agglomeration and surface activity, can be used as a carrier for preparing a carbon nano tube catalyst, and can greatly promote the controllable preparation and wide application of the carbon nano tube.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a catalyst carrier carbon material for preparing carbon nanotubes and a preparation method and application thereof.
Background
The catalyst is one of the essential raw materials in the synthesis process of the carbon nano tube, and the type, the chemical property, the particle size, the distribution and the like of the catalyst are important factors for controlling the morphology and the structure of the carbon nano tube. For the same catalyst, the particle size of the catalyst is a key factor for controlling the diameter of the carbon nanotube. Hafner et al believe that nucleation and growth of single-walled carbon nanotubes thereon is more favored when the catalyst size is less than 3nm, and as the catalyst particle size increases, the catalyst surface tends to coat with carbon resulting in "deactivation" of the catalyst or growth of multi-walled carbon nanotubes, and even carbon fibers.
On one hand, the 'inactivation' of the catalyst seriously reduces the yield of the carbon nano tube, and meanwhile, the carbon-coated catalyst is difficult to remove in the subsequent purification process and remains in the finished product of the carbon nano tube, so that the impurity content is high, the practical application of the carbon nano tube is influenced, and the carbon nano tube is particularly used as a battery conductive additive.
The use of different carriers to fix catalysts with uniform particle size distribution is a common idea for the synthesis of high quality carbon nanotubes. For example, a high density carbon nanotube array can be obtained by supporting uniform, nano-scale catalyst particles on a substrate (e.g., chinese patent application CN102502589A, CN 101077773A). In addition, the porous carrier is an effective means for mass production of carbon nanotube powder, including carbon-based materials.
The carbon material is used as a catalyst carrier and has been reported in related technologies at home and abroad. The carbon material described herein relates to a single component or a composite of two components of porous carbon black, ketjen black, graphene and derivatives thereof, and also to a carbon material obtained by carbonizing a polymer. The above materials are subject to one or more of the following problems: (1) the preparation process is carried out at high temperature, the temperature is not equal to 500-2000 ℃, even exceeds 2000 ℃, and the danger and the energy consumption are serious (for example, Chinese patent applications CN105073260A, CN106876729B and CN 109935846A); (2) the polymer needs to be subjected to small molecule polymerization reaction in the early stage of carbonization, the synthesis steps are complicated, and a large amount of small molecules such as initiator and monomer remain (for example, Chinese patent application CN 106876729B); (3) the surface is inert in chemical reaction, the activity is low, the loading of the catalyst is mainly dependent on defect sites randomly distributed on the surface, the loading rate and the loading uniformity are not controllable, and other surface modifiers are generally needed (for example, Chinese patent application CN 109935846A); (4) the carrier is agglomerated in the process of removing the solvent or synthesizing the carbon nano tube, so that the surface actually utilized is greatly reduced.
Therefore, a simple and efficient carbon material with a high specific surface, a low possibility of agglomeration and an active surface is found to be used as a carrier of the carbon nanotube catalyst, is very important for preparing high-quality carbon nanotubes in batch, and can greatly promote the controllable preparation and wide application of the carbon nanotubes. In addition, the catalyst has reference significance for other catalysis fields such as fuel cells, industrial catalysis and the like.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The main purpose of the present invention is to overcome at least one of the above drawbacks of the prior art, and to provide a carbon material as a catalyst carrier for preparing carbon nanotubes, and a preparation method and applications thereof, so as to solve the problems of complicated preparation process, uncontrollable loading rate and loading uniformity, and easy agglomeration of the existing catalyst carbon carrier.
In order to achieve the purpose, the invention adopts the following technical scheme:
a first aspect of the present invention provides a method for producing a carbon material, comprising: providing a conductive particle intercalated graphene oxide dispersion liquid; and granulating the graphene oxide dispersion liquid of the conductive particle intercalation layer to remove a solvent, thereby obtaining the carbon material.
According to one embodiment of the present invention, the graphene oxide dispersion liquid for conductive particle intercalation is obtained by the following steps: dispersing graphene oxide in a first solvent to obtain a graphene oxide dispersion liquid; dispersing the conductive particles in a second solvent to obtain a conductive particle dispersion liquid; and fully mixing the graphene oxide dispersion liquid and the conductive particle dispersion liquid to obtain the graphene oxide dispersion liquid of the conductive particle intercalation.
According to one embodiment of the invention, the thorough mixing comprises mixing by homogenizing and/or grinding, wherein the pressure of the homogenizing is 1000 bar-1200 bar, the flow rate is 0.1 mL/s-5 mL/s, and the processing time is 20 min-60 min.
According to one embodiment of the invention, the concentration of the graphene oxide dispersion liquid is 0.05 mg/mL-40 mg/mL, and the conductive particles account for 1% -30% of the total mass of the graphene oxide and the conductive particles; the conductive particles are selected from one or more of carbon black, ketjen black, onion carbon and fullerene.
According to an embodiment of the present invention, the first solvent and the second solvent are each independently selected from one or more of water, an aromatic solvent, and a low molecular alcohol solvent having not more than 3 carbon atoms; the first solvent and/or the second solvent also comprises a surfactant, and the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane and gamma-aminopropyltriethoxysilane.
According to one embodiment of the invention, the dispersion is subjected to the granulation desolventization by spray drying at a treatment pressure of 0.1 to 0.5MPa, at a treatment temperature of 120 to 200 ℃ and at a treatment flow rate of 800 to 1500 mL/h.
In a second aspect of the present invention, there is provided a carbon material having a spheroidal or spherical structure formed by aggregating carbon sheets composed of graphene oxide intercalated with a plurality of layers of conductive particles.
According to one embodiment of the present invention, the inner part of the spheroidal or spherical structure has nanopores, and the specific surface area of the carbon material is 10m2/g～350m2The grain diameter of the carbon material is 0.1-100 mu m; the carbon sheet comprises 1-10 layers of graphene oxide.
A third aspect of the present invention provides a catalyst carrier using the aforementioned carbon material.
The fourth aspect of the invention provides the application of the catalyst carrier in the preparation of carbon nanotubes and composites thereof.
According to the technical scheme, the invention has the beneficial effects that:
the invention provides a novel carbon material and a preparation method thereof, and the carbon material with excellent load performance is obtained by adopting a specific process to obtain a graphene oxide dispersion liquid of a conductive intercalation and granulating to remove a solvent. The method has simple process and low cost, and the prepared carbon material has excellent comprehensive performance of high specific surface area, difficult agglomeration and active surface, can be used as a carrier for preparing a carbon nano tube catalyst, can greatly promote the controllable preparation of the carbon nano tube and a composite material thereof, and has good application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a flow chart of a process for preparing a carbon material according to one embodiment of the present invention;
FIG. 2 is a scanning electron micrograph of the carbon material of example 1;
FIG. 3 is an X-ray diffraction pattern of the carbon material of example 1;
FIG. 4 is a Raman spectrum of the carbon material of example 1;
FIG. 5 is an X-ray photoelectron spectrum of the carbon material of example 1;
FIG. 6 is a scanning electron micrograph of a carbon material of comparative example 1;
fig. 7 is a scanning electron microscope image of the graphene carbon nanotube composite material of application example 1;
fig. 8a and 8b are transmission electron micrographs of the graphene carbon nanotube composite material of application example 1, respectively;
FIG. 9 is a transmission electron micrograph of catalyst nanoparticles formed in application example 1;
fig. 10 is a statistical distribution diagram of the particle diameters of the catalyst nanoparticles formed in application example 1.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
A first aspect of the present invention provides a method for producing a carbon material, the method comprising: providing a conductive particle intercalated graphene oxide dispersion liquid; and granulating the graphene oxide dispersion liquid of the conductive particle intercalation to remove a solvent to obtain the carbon material.
Fig. 1 shows a flow chart of a process for producing a carbon material according to an embodiment of the present invention, and as shown in fig. 1, in the present embodiment, the method for producing a carbon material includes: dispersing graphene oxide in a first solvent to obtain a graphene oxide dispersion liquid; dispersing the conductive particles in a second solvent to obtain a conductive particle dispersion liquid; fully mixing the graphene oxide dispersion liquid and the conductive particle dispersion liquid to obtain a conductive particle intercalated graphene oxide dispersion liquid; and granulating the graphene oxide dispersion liquid of the conductive particle intercalation to remove a solvent to obtain the carbon material.
According to the invention, in the synthesis process of the carbon nano tube, the particle size of the catalyst is a key factor for controlling the tube diameter of the carbon nano tube, and the fixation of the catalyst with uniform particle size distribution by using different catalyst carriers is a common idea for synthesizing the high-quality carbon nano tube, so that the selection of the catalyst carrier plays an important role in the quality of the synthesized carbon nano tube. The commonly used catalyst carrier is a carbon material, however, the existing catalyst carbon carrier has complex preparation process and harsh reaction conditions; or the load rate and load uniformity of the obtained carrier are not controllable; or easy to agglomerate, greatly reducing the practical utilization surface. The inventor of the invention finds that the carbon composite material with a multistage assembly structure can be prepared by a simple and low-cost process method, and the carbon material can effectively improve the efficiency and quality of catalyst loading.
Specifically, the carbon material preparation process disclosed by the invention firstly prepares the graphene oxide dispersion liquid for conductive particle intercalation, utilizes the high monolayer rate and high surface activity of the graphene oxide, and simultaneously enables the dispersion liquid to still maintain a higher specific surface after the solvent is removed by the conductive particle intercalation technology, so that the collapse and damage of the structure due to agglomeration are avoided. And continuously granulating to remove the solvent on the basis, so that the dried material forms a sphere-like structure with folds macroscopically while microscopically not agglomerating, and further exposes and fixes an active surface capable of being loaded by the catalyst. In addition, because the drying temperature is low, the preparation process has no high temperature, most of oxygen-containing groups of the catalyst are reserved, a large number of active sites are provided for capturing the catalyst, and the efficiency and the quality of the catalyst loading are improved.
The method for producing the carbon material of the present invention will be specifically described below with reference to FIG. 1.
Firstly, Graphene Oxide (GO) is dispersed in a first solvent to obtain a graphene oxide dispersion liquid.
The graphene oxide can be graphene oxide powder or a filter cake, or a graphene oxide pre-dispersion liquid which is pre-dispersed to a certain extent. Dispersing the graphene oxide in a first solvent, such as water, an aromatic solvent, or a solvent having not more than 3 carbon atoms (n)C3) or less, for example, ethanol, propanol, etc. The concentration of the graphene oxide dispersion is 0.05mg/mL to 40mg/mL, for example, 0.05mg/mL, 0.1mg/mL, 1mg/mL, 10mg/mL, 15mg/mL, 20mg/mL, 30mg/mL, or the like. In order to make the graphene oxide more dispersible, a proper amount of surfactant, including but not limited to one or more of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and gamma-aminopropyltriethoxysilane (KH-550), may be further added to the first solvent.
Next, the conductive particles are dispersed in a second solvent to obtain a conductive particle dispersion liquid.
The conductive particles are selected from one or more of carbon black, ketjen black, onion carbon and fullerene. The conductive particle dispersion liquid can be obtained by mixing and dispersing the conductive particle dispersion liquid and a soluble second solvent according to a certain proportion. Wherein the second solvent can be water, aromatic solvent, and carbon number not more than 3 (n)C3) or less, for example, ethanol, propanol, etc. The conductive particles account for 1% to 30% of the total mass of the graphene oxide and the conductive particles, for example, 1%, 5%, 10%, 15%, 20%, 30%, and the like. Similarly, a suitable amount of a surfactant, including but not limited to one or more of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), and gamma-aminopropyltriethoxysilane (KH-550), may also be added to the second solvent.
In some embodiments, the dispersion of the graphene oxide and the dispersion of the conductive particles may be performed by a dispersion apparatus such as an ultrasonic dispersion apparatus, a high-speed dispersion tray, or an emulsifying machine.
Further, after the two dispersions were obtained, the two were thoroughly mixed. The mixing apparatus may be a homogenizer, a centrifugal mill, or a combination thereof, to which the present invention is not limited. In the homogenizing treatment, the pressure of the homogenizing treatment is generally 1000bar to 1200bar, for example, 1000bar, 1100bar, 1150bar, 1180bar, 1200bar, etc., the flow rate is 0.1mL/s to 5mL/s, for example, 0.1mL/s, 0.8mL/s, 1mL/s, 2mL/s, 2.5mL/s, 3mL/s, etc., and the treatment time is 20min to 60min, for example, 20min, 30min, 50min, 55min, 60min, etc. And mixing to obtain a graphene oxide dispersion liquid of the conductive particle intercalation, and further granulating to remove the solvent to obtain the carbon material.
The graphene oxide dispersion liquid intercalated by the conductive particles can still maintain a higher specific surface area after solvent removal treatment, and is not easy to agglomerate. Preferably, the desolventizing is carried out by a spray drying technique, which ensures that the material does not agglomerate microscopically, and simultaneously enables the material to take on a macroscopically wrinkled spheroidal or spherical structure, further exposing and fixing the active surface on which the catalyst can be supported.
In some embodiments, the foregoing spray drying is conducted at a pressure of 0.1MPa to 0.5MPa, e.g., 0.1MPa, 0.3MPa, 0.4MPa, 0.5MPa, etc., at a flow rate of 800mL/h to 1500mL/h, e.g., 800mL/h, 900mL/h, 1000mL/h, 1200mL/h, 1500mL/h, etc., and at a temperature of 120 ℃ to 200 ℃, e.g., 120 ℃, 130 ℃, 150 ℃, 180 ℃, etc. Due to the low drying temperature, most of oxygen-containing groups of the material are reserved, a large number of active sites are provided for capturing the catalyst, and the efficiency and the quality of the catalyst loading are further improved.
The carbon material prepared by the method is in a sphere-like or spherical structure, wherein the sphere-like or spherical structure is formed by aggregating a plurality of layers of thin and flexible carbon sheets, the carbon sheets are formed by graphene oxide intercalated by conductive particles, and a large number of nano-pore channels are arranged in the carbon sheets. The X-ray diffraction represents a 002 diffraction peak of graphite, each carbon sheet approximately comprises graphene oxide with the thickness of 1-10 layers, wherein the higher the oxidation degree is, the thinner the number of layers of the graphene oxide is, and oxygen-containing groups on the surface provide more active sites to adsorb conductive particles, so that stacking of the graphene oxide sheet layers in the reduction process is inhibited, and on the other hand, more loading sites can be provided for the catalyst, and the utilization efficiency of the carrier is improved.
The carbon material contains a large number of oxygen-containing groups in addition to C in an X-ray photoelectron spectrum, and the carbon material is proved to have chemical activity. The carbon material has obvious defect peaks in Raman spectrum, and the defects are beneficial to better dispersing the loaded substance on the surface of the material when the carbon material is used as a carrier.
In some embodiments, the carbon material has a specific surface area of 10m2/g～350m2In g, e.g. 10m2/g、50m2/g、100m2/g、230m2/g、290m2And/g, the particle diameter of the carbon material is 0.1 to 100. mu.m, for example, 0.1, 1, 10, 50, 70, 90, 100 μm. The high specific surface area of the material can ensure higher loading rate of the carbon material.
In conclusion, the carbon material with excellent loading performance is obtained by a simple and low-cost mode, has excellent comprehensive performance of simple preparation process, high specific surface area, difficult agglomeration and surface activity, can be used as a carrier for preparing a carbon nanotube catalyst, effectively solves the problems of inactivation and particle size distribution of the carbon nanotube catalyst, is very important for preparing high-quality carbon nanotubes in batches, and can greatly promote the controllable preparation and wide application of the carbon nanotubes. In addition, the catalyst has reference significance for other catalysis fields such as fuel cells, industrial catalysis and the like.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, reagents, materials and the like used in the present invention are commercially available.
Example 1
1) And (3) taking 4g of graphene oxide and 500mL of deionized water, and uniformly blending the graphene oxide and the deionized water by a mechanical stirrer at the rotating speed of 3000rpm for 30min to prepare a graphene oxide coarse dispersion liquid of 8 mg/mL.
2) 0.05g of ketjen black and 20ml of deionized water were taken and uniformly blended by magnetic stirring at a rotation speed of 200rpm for 30min to prepare a crude dispersion of conductive particles.
3) And adding the coarse dispersion liquid of the conductive particles into the graphene oxide coarse dispersion liquid, and processing the graphene oxide coarse dispersion liquid by using an ultracentrifugal grinder, wherein the rotating speed of the ultracentrifugal grinder is 15000rpm, and the processing time is 20min, so as to prepare the graphene oxide mixed dispersion liquid with the conductive particle intercalation.
4) And (3) granulating the graphene oxide mixed dispersion liquid intercalated with the conductive particles by using spray drying equipment to remove a solvent, wherein the treatment pressure of the spray drying equipment is 0.2MPa, the treatment flow rate is 1500ml/h, the treatment temperature is 140 ℃, and finally the carbon material is prepared.
FIG. 2 is a scanning electron micrograph of the carbon material of example 1, and it can be seen from FIG. 2 that the carbon material has a spheroidal structure and a particle diameter of about 5 μm. The carbon material has a specific surface area of 300m2/g。
FIG. 3 is an X-ray diffraction pattern (XRD) of the carbon material of example 1, having a 002 diffraction peak of graphite. FIG. 4 is a Raman spectrum of the carbon material of example 1, and it can be seen from FIG. 4 that there is a significant defect peak in the Raman spectrum, ID/IG1.02. Fig. 5 shows an X-ray photoelectron spectroscopy (XPS) of the carbon material of example 1, and it can be seen from fig. 5 that the carbon material contains a large amount of oxygen-containing groups in addition to C and has chemical activity.
Example 2
1) And (3) taking 6g of graphene oxide and 500mL of KH-550, and uniformly blending the graphene oxide and the KH-550 by magnetic stirring, wherein the rotating speed is 500rpm, and the treatment time is 60min, so as to prepare a 12mg/mL coarse graphene oxide dispersion.
2) 0.2g of onion carbon and 25ml of deionized water are taken and are uniformly blended by magnetic stirring, the rotating speed is 200rpm, the processing time is 30min, and the coarse dispersion liquid of the conductive particles is prepared.
3) And adding the coarse dispersion liquid of the conductive particles into the graphene oxide coarse dispersion liquid, and treating the graphene oxide coarse dispersion liquid by using a high-pressure homogenizer, wherein the treatment pressure is 1200bar, and the flow rate is 0.5mL/s for 15min, so as to prepare the graphene oxide mixed dispersion liquid of the conductive particle intercalation.
4) And (3) granulating the graphene oxide mixed dispersion liquid intercalated with the conductive particles by using spray drying equipment to remove a solvent, wherein the treatment pressure of the spray drying equipment is 0.3MPa, the treatment flow rate is 1200ml/h, the treatment temperature is 160 ℃, and finally the carbon material is prepared.
Example 3
1) And (3) taking 10g of graphene oxide and 500mL of deionized water, and uniformly blending the graphene oxide and the deionized water by a mechanical stirrer at the rotation speed of 4000rpm for 40min to prepare a 20mg/mL graphene oxide coarse dispersion.
2) 0.5g of carbon black, 1g of sodium dodecyl benzene sulfonate and 30ml of deionized water are taken and uniformly blended by magnetic stirring, the rotating speed is 500rpm, the processing time is 30min, and the coarse dispersion liquid of the conductive particles is prepared.
3) And adding the coarse dispersion liquid of the conductive particles into the graphene oxide coarse dispersion liquid, and treating the graphene oxide coarse dispersion liquid by using a micro-jet homogenizer, wherein the treatment pressure is 1000bar, and the flow rate is 0.5mL/s for 30min, so as to prepare the graphene oxide mixed dispersion liquid of the conductive particle intercalation.
4) And (3) granulating the graphene oxide mixed dispersion liquid intercalated with the conductive particles by using spray drying equipment to remove a solvent, wherein the treatment pressure of the spray drying equipment is 0.4MPa, the treatment flow rate is 1000ml/h, the treatment temperature is 150 ℃, and finally the carbon material is prepared.
Comparative example 1
A carbon material was prepared by the method of example 1 except that the conductive particles were not added, i.e.:
1) and (3) taking 4g of graphene oxide and 500mL of deionized water, and uniformly blending the graphene oxide and the deionized water by a mechanical stirrer at the rotating speed of 3000rpm for 30min to prepare a graphene oxide coarse dispersion liquid of 8 mg/mL.
2) And (3) granulating the graphene oxide mixed dispersion liquid by using spray drying equipment to remove a solvent, wherein the treatment pressure of the spray drying equipment is 0.2MPa, the treatment flow rate is 1500ml/h, and the treatment temperature is 140 ℃, so that the carbon material is obtained.
Characterizing the carbon material and comparing it with example 1, fig. 6 is a scanning electron micrograph of the carbon material of comparative example 1, from which fig. 6 it was found that the uniformity of the particle size of the resulting spherical particles was reduced and that there were irregular carbon clusters which were partially non-spherical, the individual particle size being over 10 μm; the corresponding specific surface area was measured to be 210m2(ii) in terms of/g. Therefore, the intercalation of the conductive particles is helpful for inhibiting the stacking of the graphene oxide sheets, the uniformity of sheet dispersion is improved, the obtained carbon particles are more regular and uniform in spherical shape and narrow in particle size distribution, and the specific surface area is correspondingly increased. In addition, the conductive particles are not added, the yield of the spray-dried powder is only 38%, the yield of the spray-dried powder is maintained to be more than 90%, and the cost is greatly reduced.
Application example 1
The carbon materials of example 1 were used as catalyst supports, respectively, to prepare carbon nanotube composites.
Specifically, a carbon material was charged into a quartz tube, and hydrogen gas and argon gas were simultaneously introduced at a flow rate of 300sccm, respectively, so that the carbon material was stably suspended in the quartz tube under a gas flow. Heating a fluidized bed reaction cavity to 450 ℃, introducing 100sccm Ar gas as a carrier gas, carrying ferrocene and ethanol into the reaction cavity through a supersaturated ferrocene ethanol solution with a constant temperature of 60 ℃ by a bubbling method, and then carrying out thermal cracking to form pre-carbonized iron (Fe) catalyst nanoparticles attached to the surface of the carbon material carrier, wherein the bubbling duration is 20 minutes. Then, the temperature of the fluidized bed reaction chamber is raised to 700 ℃, hydrogen gas and argon gas are respectively introduced at the same time at the flow rate of 300sccm, then carbon monoxide is introduced at the flow rate of 100sccm as a carbon source, and after 30 minutes, the carbon monoxide gas is closed. Stopping the reaction, waiting for the equipment to cool to room temperature, and then closing all the gas to obtain the graphene carbon nanotube composite material with the sea urchin-like structure, wherein the graphene carbon nanotube composite material comprises a graphene microsphere and a plurality of carbon nanotubes formed on the surface of the graphene microsphere, the graphene microsphere is formed by gathering a plurality of layers of thin and flexible carbon sheets, each carbon sheet is formed by a plurality of layers of reduced graphene oxide, and a nanopore is formed in the graphene microsphere.
Fig. 7 is a scanning electron microscope image of the graphene carbon nanotube composite material in application example 1, the graphene carbon nanotube composite material is sea urchin-like, and carbon nanotubes with lengths of tens of micrometers are dispersedly grown on the surface of graphene microspheres, and are lapped with carbon nanotubes on other graphene microspheres to form a continuous conductive network. Fig. 8a and 8b are transmission electron micrographs of the graphene carbon nanotube composite material of application example 1, respectively, and it can be seen from fig. 8a and 8b that the carbon nanotubes prepared under the conditions are single-walled carbon nanotubes with a tube diameter of 1nm to 3 nm.
Fig. 9 is a transmission electron microscope image of the catalyst nanoparticles formed in application example 1, and fig. 10 is a statistical distribution diagram of particle diameters of the catalyst nanoparticles formed in application example 1. As can be seen from fig. 9 and 10, the catalyst nanoparticles on the surface of the graphene oxide are uniformly distributed, the average particle diameter is 1.78nm, and more than 95% of the particles have a diameter less than 3nm, which is beneficial to preparing the single-walled carbon nanotube with a relatively small tube diameter.
Therefore, the carbon material can be used as a catalyst carrier for growing the carbon nanotube composite material, and when the carbon material is used as the catalyst carrier, the particle size of the loaded catalyst is proper and is uniformly distributed, so that the quality of the grown carbon nanotube can be effectively improved, and the controllable preparation and application of the carbon nanotube are promoted. It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
1. A method for producing a carbon material, comprising:
providing a conductive particle intercalated graphene oxide dispersion liquid; and
and granulating the graphene oxide dispersion liquid of the conductive particle intercalation to remove a solvent to obtain the carbon material.
2. The preparation method according to claim 1, wherein the graphene oxide dispersion liquid for conductive particle intercalation is obtained by:
dispersing graphene oxide in a first solvent to obtain a graphene oxide dispersion liquid;
dispersing the conductive particles in a second solvent to obtain a conductive particle dispersion liquid; and
and fully mixing the graphene oxide dispersion liquid and the conductive particle dispersion liquid to obtain the graphene oxide dispersion liquid of the conductive particle intercalation.
3. The method of claim 2, wherein the thoroughly mixing comprises mixing by homogenizing and/or grinding, wherein the homogenizing is performed at a pressure of 1000bar to 1200bar, a flow rate of 0.1mL/s to 5mL/s, and a treatment time of 20min to 60 min.
4. The preparation method according to claim 2, wherein the concentration of the graphene oxide dispersion liquid is 0.05mg/mL to 40mg/mL, and the conductive particles account for 1% to 30% of the total mass of the graphene oxide and the conductive particles; the conductive particles are selected from one or more of carbon black, ketjen black, onion carbon and fullerene.
5. The method according to claim 2, wherein the first solvent and the second solvent are each independently selected from one or more of water, an aromatic solvent, and a low molecular alcohol solvent having not more than 3 carbon atoms; the first solvent and/or the second solvent also comprises a surfactant, and the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, sodium lignosulfonate, polyvinyl alcohol, polydimethylsiloxane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane and gamma-aminopropyltriethoxysilane.
6. The preparation method according to claim 1, wherein the dispersion is subjected to the granulation desolventizing by spray drying at a treatment pressure of 0.1 to 0.5MPa, a treatment temperature of 120 to 200 ℃ and a treatment flow rate of 800 to 1500 mL/h.
7. A carbon material produced by the method according to any one of claims 1 to 6, wherein the carbon material has a spheroidal or spherical structure formed by aggregating carbon sheets composed of graphene oxide intercalated with a plurality of layers of conductive particles.
8. The carbon material according to claim 7, wherein the spheroidal or spherical structure has nanopores inside, and the carbon material has a specific surface area of 10m2/g～350m2The carbon material has a particle diameter of 0.1 to 100 [ mu ] m; the carbon sheet comprises 1-10 layers of graphene oxide.
9. A catalyst carrier using the carbon material as claimed in any one of claims 7 to 8.
10. Use of the catalyst support according to claim 9 for the preparation of carbon nanotubes and composites thereof.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101348249A (en) * | 2008-09-05 | 2009-01-21 | 清华大学 | Method for preparing carbon nano-tube array on particle interior surface |
| US20140030590A1 (en) * | 2012-07-25 | 2014-01-30 | Mingchao Wang | Solvent-free process based graphene electrode for energy storage devices |
| CN108367914A (en) * | 2015-07-20 | 2018-08-03 | 纳米技术仪器公司 | Height-oriented graphene oxide membrane and the production by its derivative graphite film |
| CN111470491A (en) * | 2020-04-13 | 2020-07-31 | 北京石墨烯研究院有限公司 | Carbon hybrid powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101348249A (en) * | 2008-09-05 | 2009-01-21 | 清华大学 | Method for preparing carbon nano-tube array on particle interior surface |
| US20140030590A1 (en) * | 2012-07-25 | 2014-01-30 | Mingchao Wang | Solvent-free process based graphene electrode for energy storage devices |
| CN108367914A (en) * | 2015-07-20 | 2018-08-03 | 纳米技术仪器公司 | Height-oriented graphene oxide membrane and the production by its derivative graphite film |
| CN111470491A (en) * | 2020-04-13 | 2020-07-31 | 北京石墨烯研究院有限公司 | Carbon hybrid powder and preparation method thereof |
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