CN111422857A - Graphene nano-bubble material, preparation method and application thereof, adsorbent, catalyst, optical material and energy storage material - Google Patents
Graphene nano-bubble material, preparation method and application thereof, adsorbent, catalyst, optical material and energy storage material 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
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention provides a graphene nano-bubble material, a preparation method and application thereof, an adsorbent, a catalyst, an optical material and an energy storage material. The preparation method of the graphene nano bubble material comprises the following steps: (a) heating and reacting a graphite raw material with oxidizing acid; (b) heating and reacting a product obtained by the reaction in the step (a) with an intercalation agent; (c) heating and reacting the product obtained in the step (b) with an expanding agent, and carrying out solid-liquid separation after reaction to obtain a graphite nano bubble material; (d) and carrying out mechanical force treatment on the graphite nano bubble material to obtain the graphene nano bubble material. The method has the advantages of scientific process, simplicity and feasibility, no need of expensive equipment and noble metal as reaction conditions, higher yield of the obtained graphene nano bubble material, larger bubble size, diameter of between 100 and 300nm, closed bubble, easily controlled preparation process, wide raw material source, preparation cost of less than 1.5 g/yuan, and suitability for batch production.
Description
Technical Field
The invention relates to the field of inorganic materials, in particular to a graphene nano-bubble material, a preparation method and application thereof, an adsorbent, a catalyst, an optical material and an energy storage material.
Background
Bubbles are a common phenomenon in daily life, and for bubbles visible to the naked eye, the formation and properties of the bubbles are quite mature regardless of experiments or theories, and the research on the bubbles invisible to the naked eye and even nano-scale bubbles is relatively deficient. With the development of technology, the concept of nanobubbles was proposed in the last 80 th century. Many researchers have studied nanobubbles afterwards, and there are some breakthrough achievements.
Since 2004, graphene materials became available, and since then, graphene has attracted much attention in its unique structure and properties. When studying the covering of 2D materials, researchers found that single-layer or multi-layer graphene can bind some gas molecules to form a convex shape, which is called graphene nanobubble.
The preparation method of the graphene nanobubble comprises high-temperature proton bombardment, mechanical stripping and covering, high-temperature dissociation, cooling, electrochemistry and the like. At present, few articles and patents related to graphene nanobubbles exist, and in further research on the change of the forming mechanism and the material property, researchers find some peculiar phenomena that the nanobubbles covered by graphene can move transmission substances, the pressure inside the nanobubbles is up to several Gpa, and the nanobubbles are considered to have potential application value in the field of nonlinear optical materials.
The m.f. crommie group at the university of california at 2010, berkeley, adopts a cooling method to obtain graphene nanobubbles (the size is larger than 3nm) when graphene grows on the platinum surface at a high temperature, and the preparation method is harsh in conditions, needs to depend on expensive metals, has high requirements on instruments and equipment, and has small size of the prepared bubbles. In 2016, E.Khestanova et al transfer graphene to the surface of a layered material, and a bubble structure can be generated under well-controlled conditions, but the yield of bubbles prepared by the method is not high, and the method has multiple steps and is difficult to control.
Chinese patent (CN201910302265.X) discloses a method for preparing a graphene bubble material, which comprises the steps of cleaving graphite by using an adhesive tape, attaching the graphite to the surface of a substrate treated by oxygen plasma, and carrying out heat treatment and liquid nitrogen low-temperature cooling on the substrate to obtain graphene bubbles. This method requires the use of expensive equipment and is difficult to mass produce for researchers to further study its properties.
In the article "macro' bubble film template-oriented-ordered-arrangement for high-rate supercapacitors", a template induction method is proposed by professor chening yangcheng in 2012 to prepare a Macroporous "bubble" graphene film, and bubbles of the bubble graphene film prepared by the method are in an open state but not in a closed state. Similarly, Chinese patent (CN104627995B) discloses a foamed graphene material and a preparation method thereof, in the method, oxalic acid and graphene oxide dispersion liquid are dissolved according to a proportion, and are dried and then treated at a high temperature of 400-1000 ℃ in a protective gas atmosphere, and finally the foamed graphene material is obtained by hydrazine hydrate steam reduction at a temperature of 100-200 ℃.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a graphene nano-bubble material, the method has a scientific, simple and feasible process, expensive equipment and precious metal are not required as reaction conditions, the obtained graphene nano-bubble material has high yield, large bubble size, a diameter of between 100 and 300nm, closed bubbles, easily controlled preparation process, wide raw material source and preparation cost of less than 1.5 g/yuan, and is suitable for batch production.
The second purpose of the invention is to provide the graphene nano-bubble material obtained by the preparation method.
The third purpose of the invention is to provide an application of the graphene nano bubble material.
A fourth object of the present invention is to provide an adsorbent, a catalyst, an optical material or an energy storage material.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides a preparation method of a graphene nanobubble material, which comprises the following steps:
(a) heating and reacting a graphite raw material with oxidizing acid;
(b) heating and reacting a product obtained by the reaction in the step (a) with an intercalation agent;
(c) heating and reacting the product obtained in the step (b) with an expanding agent, and carrying out solid-liquid separation after reaction to obtain a graphite nano bubble material;
(d) and carrying out mechanical force treatment on the graphite nano bubble material to obtain the graphene nano bubble material.
As a further preferable technical solution, the graphite raw material includes at least one of flake graphite, expandable graphite, or expanded graphite.
As a further preferable embodiment, the oxidizing acid includes at least one of concentrated sulfuric acid, concentrated nitric acid, perchloric acid, hypochloric acid, or permanganic acid;
preferably, the intercalant comprises K2Cr2O7、H2O2、KMnO4、(NH4)2S2O8、O3、CrO3Or K2FeO4At least one of;
preferably, the swelling agent comprises (NH)4)2C2O4、H2O2、(NH4)2S2O8、H2C2O4、NH4HCO3Or NH4NO3At least one of;
preferably, the intercalant and the expansion agent are different.
As a further preferable technical scheme, the mass ratio of the graphite raw material, the oxidizing acid, the intercalating agent and the expanding agent is 1: (18-108): (0.1-1): (5-60), preferably 1: (45-55): (0.2-0.8): (5-20), more preferably 1: 50: 0.5: 10.
as a further preferable technical scheme, in the step (a), the heating reaction temperature is 0-50 ℃, and the reaction time is 10min-4 h;
preferably, in the step (b), the heating reaction temperature is 0-60 ℃, and the reaction time is 30min-10 h;
preferably, in step (c), the heating reaction temperature is 0-40 ℃ and the reaction time is 1min-1 h.
As a further preferable technical scheme, after solid-liquid separation, the method further comprises the steps of washing and drying in sequence, and then the graphite nano-bubble material is obtained;
preferably, the drying temperature is 30-120 ℃ and the drying time is 3-12 h.
In a further preferred embodiment, the mechanical treatment method includes at least one of an ultrasonic method, a ball milling method, a high shear emulsification dispersion method, a high pressure homogenization method, a jet milling method, a super-gravity rotation method, a supercritical fluid method, and a microfluidization method.
In a second aspect, the invention provides a graphene nano-bubble material obtained by the preparation method.
In a third aspect, the invention provides an application of the graphene nanobubble material in preparation of an adsorbent, a catalyst, an optical material or an energy storage material.
In a fourth aspect, the present invention provides an adsorbent, a catalyst, an optical material or an energy storage material, including the graphene nanobubble material.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the graphene nano-bubble material, the graphite raw material sequentially reacts with the oxidizing acid, the intercalating agent and the expanding agent in a heating manner, the oxidizing acid firstly intercalates the graphite raw material, then the intercalating agent realizes the effect of oxidizing intercalation in an oxidizing acid system, and the interlayer spacing of the graphite raw material is opened; and reacting with an expanding agent to generate gas in a reaction system, wherein part of the gas enters the interlayer space of the opened graphite raw material and is bound by the graphite material, meanwhile, along with the expansion of the graphite raw material, the bound gas forms bubbles, the graphite nano-bubble material is obtained after solid-liquid separation, and then the graphite nano-bubble material is subjected to mechanical force treatment to convert the graphite nano-bubble material into the graphene nano-bubble material.
The method is scientific in process, simple and feasible, the required bubbles can be formed only by heating reaction without expensive equipment or noble metal as reaction conditions, the obtained graphene nano-bubble material is high in yield, large in bubble size, and closed in bubble diameter of between 100 and 300nm, the preparation process is easy to control, the raw material source is wide, the preparation cost is lower than 1.5 g/yuan, and the method is suitable for batch production.
Drawings
FIG. 1 is an SEM image of an intermediate graphite nanobubble material obtained in example 1;
fig. 2 is an SEM image of the graphene nanobubble material obtained in example 1;
fig. 3 is a Raman spectrum of the graphene nanobubble material obtained in example 1;
fig. 4 is an XRD pattern of the graphene nanobubble material obtained in example 1;
FIG. 5 is an SEM image of the intermediate graphite nanobubble material obtained in example 4;
FIG. 6a is an SEM image of intermediate graphite nanobubble material obtained in example 5;
FIG. 6b is an SEM image of intermediate graphite nanobubble material obtained in example 6;
FIG. 6c is an SEM image of intermediate graphite nanobubble material obtained in example 7;
FIG. 6d is an SEM image of intermediate graphite nanobubble material obtained in example 8;
FIG. 7a is an SEM image of intermediate graphite nanobubble material obtained in example 9;
FIG. 7b is an SEM image of intermediate graphite nanobubble material obtained in example 10;
FIG. 7c is an SEM image of intermediate graphite nanobubble material obtained in example 11;
FIG. 8a is an SEM image of intermediate graphite nanobubble material obtained in example 12;
FIG. 8b is an SEM image of intermediate graphite nanobubble material obtained in example 13;
FIG. 8c is an SEM image of intermediate graphite nanobubble material obtained in example 14;
FIG. 9a is an SEM image of intermediate graphite nanobubble material obtained in example 15;
FIG. 9b is an SEM image of intermediate graphite nanobubble material obtained in example 16;
FIG. 9c is an SEM image of intermediate graphite nanobubble material obtained in example 17.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
According to an aspect of the present invention, in at least one embodiment, there is provided a method for preparing a graphene nanobubble material, including the steps of:
(a) heating and reacting a graphite raw material with oxidizing acid;
(b) heating and reacting a product obtained by the reaction in the step (a) with an intercalation agent;
(c) heating and reacting the product obtained in the step (b) with an expanding agent, and carrying out solid-liquid separation after reaction to obtain a graphite nano bubble material;
(d) and carrying out mechanical force treatment on the graphite nano bubble material to obtain the graphene nano bubble material.
The preparation method comprises the steps of heating and reacting a graphite raw material with an oxidizing acid, an intercalating agent and an expanding agent in sequence, reacting the graphite raw material with the oxidizing acid and the intercalating agent in sequence, firstly intercalating the graphite raw material by the oxidizing acid, then realizing the effect of oxidizing intercalation in an oxidizing acid system by the intercalating agent, and opening the interlayer spacing of the graphite raw material; and reacting with an expanding agent to generate gas in a reaction system, wherein part of the gas enters the interlayer space of the opened graphite raw material and is bound by the graphite material, meanwhile, along with the expansion of the graphite raw material, the bound gas forms bubbles, the graphite nano-bubble material is obtained after solid-liquid separation, and then the graphite nano-bubble material is subjected to mechanical force treatment to convert the graphite nano-bubble material into the graphene nano-bubble material.
The method is scientific in process, simple and feasible, the required bubbles can be formed only by heating reaction without expensive equipment or noble metal as reaction conditions, the obtained graphene nano-bubble material is high in yield, large in bubble size, and closed in bubble diameter of between 100 and 300nm, the preparation process is easy to control, the raw material source is wide, the preparation cost is lower than 1.5 g/yuan, and the method is suitable for batch production.
It should be noted that:
the "graphite raw material" is natural graphite formed in nature or a graphite derivative obtained by subjecting natural graphite to a chemical reaction.
The "oxidizing acid" means that a central element other than hydrogen and oxygen in the acid exhibits strong oxidizing property in a chemical reaction.
The "intercalator" means a substance which can intrude into the interlayer of the graphite raw material and bond with carbon atoms between the layers to form a compound which does not destroy the layered structure of the graphite.
The "swelling agent" mentioned above means a material that can cause volume expansion by a physical and chemical reaction.
The "mechanical force treatment" refers to a treatment of the graphite nanobubble material by a mechanical force, which may be referred to as an external force and is a force applied to an object from the outside.
In a preferred embodiment, the graphite starting material comprises at least one of flake graphite, expandable graphite, or expanded graphite. The graphite starting material includes, but is not limited to, flake graphite, expandable graphite, expanded graphite, a combination of flake graphite and expandable graphite, a combination of expandable graphite and expanded graphite, a combination of flake graphite and expanded graphite, or a combination of flake graphite, expandable graphite and expanded graphite, and the like. The sources of the crystalline flake graphite, the expandable graphite and the expanded graphite are wide, the prices are low, and the preparation cost of the graphene nano-bubble material can be further reduced.
Preferably, the oxidizing acid comprises at least one of concentrated sulfuric acid, concentrated nitric acid, perchloric acid, hypochlorous acid, or permanganic acid. Oxidizing acids include, but are not limited to, concentrated sulfuric acid, concentrated nitric acid, perchloric acid, hypochlorous acid, permanganic acid, a combination of concentrated sulfuric acid and concentrated nitric acid, a combination of perchloric acid and hypochlorous acid, a combination of hypochlorous acid and permanganic acid, a combination of concentrated sulfuric acid, concentrated nitric acid, and perchloric acid, or a combination of perchloric acid, hypochlorous acid, and permanganic acid, and the like. The oxidizing acids have strong oxidizing property, are easy to intercalate the graphite raw material and are beneficial to reducing the reaction difficulty, thereby reducing the reaction temperature and saving energy.
The above-mentioned "concentrated sulfuric acid" means H2SO4Sulfuric acid solution with mass fraction of more than or equal to 70 percent. The above-mentioned "concentrated nitric acid" is HNO365-85% of nitric acid solution.
Preferably, the intercalant comprises K2Cr2O7、H2O2、KMnO4、(NH4)2S2O8、O3、CrO3Or K2FeO4At least one of (1). Intercalating agents include, but are not limited to, K2Cr2O7，H2O2，KMnO4，(NH4)2S2O8，O3，CrO3，K2FeO4，K2Cr2O7And H2O2KMnO4And (NH)4)2S2O8Combination of (A) and (B), O3And CrO3Combination of (A) CrO3And K2FeO4Combination of (1), K2Cr2O7、H2O2And KMnO4A combination of (A) or (B), or3、CrO3And K2FeO4Combinations of (a), (b), and the like. The intercalation agent and the oxidizing acid have better matching effect, and the interlamellar spacing of the graphite raw material can be basically and completely opened, so that the quantity of bubbles entering the interlamellar of the graphite raw material subsequently is increased.
Preferably, the swelling agent comprises (NH)4)2C2O4、H2O2、(NH4)2S2O8、H2C2O4、NH4HCO3Or NH4NO3At least one of (1). Swelling agents include, but are not limited to (NH)4)2C2O4，H2O2，(NH4)2S2O8，H2C2O4，NH4HCO3，NH4NO3，(NH4)2C2O4And H2O2Combination of (NH)4)2S2O8And H2C2O4Combination of (1), NH4HCO3And NH4NO3Combination of (NH)4)2C2O4、H2O2And (NH)4)2S2O8A combination of (A) or (H)2C2O4、NH4HCO3And NH4NO3Combinations of (a), (b), and the like. When the expanding agent is selected, the graphite raw material and the bubbles are easier to expand, and the diameters of the formed bubbles are larger.
Preferably, the intercalant and the expansion agent are different.
Preferably, the mass ratio of the graphite raw material, the oxidizing acid, the intercalation agent and the expansion agent is 1: (18-108): (0.1-1): (5-60), preferably 1: (45-55): (0.2-0.8): (5-20), more preferably 1: 50: 0.5: 10. the above mass ratio is typically, but not limited to, 1: 18: 0.1: 5. 1: 50: 0.1: 5. 1: 108: 0.1: 5. 1: 18: 0.5: 5. 1: 50: 0.5: 5. 1: 108: 0.5: 5. 1: 18: 1: 5. 1: 50: 1: 5. 1: 108: 1: 5. 1: 18: 0.1: 30 or 1: 50: 0.1: 60, etc. Tests prove that when the mass ratio of the graphite raw material, the oxidizing acid, the intercalating agent and the expanding agent is in the above range, the interlamination of the graphite is opened, the intercalation agent and the expanding agent perform interlamination reaction, and the temperature, the time and the material proportion are reasonably controlled to obtain the graphite nano-bubble material.
In a preferred embodiment, in step (a), the heating reaction temperature is 0-50 ℃ and the reaction time is 10min-4 h. The above reaction temperature is typically, but not limited to, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50 ℃ and the reaction time is typically, but not limited to, 10min, 30min, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h or 4 h.
Preferably, in the step (b), the heating reaction temperature is 0-60 ℃, and the reaction time is 30min-10 h. The above reaction temperature is typically, but not limited to, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60 ℃ and the reaction time is typically, but not limited to, 30min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10 h.
Preferably, in step (c), the heating reaction temperature is 0-40 ℃ and the reaction time is 1min-1 h. The above reaction temperature is typically, but not limited to, 0, 5, 10, 15, 20, 25, 30, 35 or 40 ℃ and the reaction time is typically, but not limited to, 1min, 10min, 20min, 30min, 40min, 50min or 1 h.
In a preferred embodiment, after solid-liquid separation, the steps of washing and drying are sequentially included, and then the graphite nanobubble material is obtained.
Preferably, the drying temperature is 30-120 ℃ and the drying time is 3-12 h. The above-mentioned drying temperature is typically, but not limited to, 30, 40, 50, 60, 70, 80, 90, 100, 110 or 120 ℃ and the drying time is typically, but not limited to, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 hours.
In a preferred embodiment, the mechanical treatment comprises at least one of sonication, ball milling, high shear emulsification dispersion, high pressure homogenization, fluid jet milling, high gravity rotation, supercritical fluid processing, or microfluidization. The mechanical treatment method includes, but is not limited to, an ultrasonic method, a ball milling method, a high shear emulsification dispersion method, a high pressure homogenization method, a jet milling method, a super-gravity rotation method, a supercritical fluid method, a microfluidization method, a combination of an ultrasonic method and a ball milling method, a combination of a high shear emulsification dispersion method and a high pressure homogenization method, a combination of a jet milling method and a super-gravity rotation method, a combination of a supercritical fluid method and a microfluidization method, a combination of an ultrasonic method, a ball milling method and a high shear emulsification dispersion method, a combination of a high pressure homogenization method, a jet milling method and a super-gravity rotation method, or a combination of a super-gravity rotation method, a supercritical fluid method and a microfluidization method.
The "ultrasonic method" refers to a treatment method using an ultrasonic action.
The "ball milling method" refers to a treatment method using a ball mill.
The "high-shear emulsification dispersion method" refers to a treatment method using a high-shear emulsification dispersion machine.
The "high-pressure homogenization method" refers to a treatment method using a high-pressure homogenizer.
The "jet milling method" refers to a treatment method using a jet milling action.
The "super-gravity rotary method" refers to a treatment method using a super-gravity rotary bed.
The "supercritical fluid method" refers to a treatment method utilizing the action of a supercritical fluid.
The "microfluidization method" refers to a processing method using a microfluidizer.
It should be noted that:
the size of the bubbles is obtained from an electron microscope image, and the size of the bubbles is obtained by selecting the sizes of 100 bubbles and carrying out statistical average.
Whether the bubbles are closed bubbles or not is determined by that the bubbles are gathered to a certain bubble range through high-energy electron beams of an electron microscope during high-power focusing, if the bubbles are slowly broken to expose graphite at the bottom, and other areas are normal, the bubbles are closed bubbles, otherwise, the bubbles are non-closed bubbles.
According to another aspect of the invention, a graphene nano-bubble material obtained by the preparation method is provided. The graphene nano-bubble material is prepared by the method, has large bubble size, is closed bubble, and is low in cost.
According to another aspect of the invention, an application of the graphene nanobubble material in preparation of an adsorbent, a catalyst, an optical material or an energy storage material is provided. The graphene nano-bubble material is applied to preparation of an adsorbent, a catalyst, an optical material or an energy storage material, so that the preparation cost of the materials can be obviously reduced, and the adsorption, catalysis, optical or energy storage effects of the materials are improved.
According to another aspect of the present invention, there is provided an adsorbent, a catalyst, an optical material or an energy storage material, including the graphene nanobubble material. The adsorbent, the catalyst, the optical material or the energy storage material comprises the graphene nano bubble material, so that the graphene nano bubble material at least has the advantages of low cost and good adsorption, catalysis, optical or energy storage effects.
It should be noted that:
the "adsorbent" refers to a substance capable of effectively adsorbing some of its components from a gas or liquid.
The "catalyst" refers to a substance which can change (increase or decrease) the chemical reaction rate of a reactant in a chemical reaction without changing the chemical equilibrium, and the mass and chemical properties of the substance are not changed before and after the chemical reaction.
The above-mentioned "optical material" is a general term for a material having certain optical properties and functions used in optical experiments and optical instruments.
The "energy storage material" refers to a functional material that stores energy by using physical or chemical changes of substances, and the stored energy can be electric energy, mechanical energy, chemical energy, thermal energy, or other forms of energy; materials used for electricity storage, heat storage, hydrogen storage, solar cells and the like broadly belong to energy storage materials, such as lithium ion battery materials, sodium ion battery materials, water system battery materials or all-vanadium redox flow battery materials. The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
A preparation method of a graphene nano-bubble material comprises the following steps:
s1, weighing 1kg of flake graphite, adding 20kg of concentrated sulfuric acid (98 wt%) and 10kg of concentrated nitric acid (67 wt%), adjusting the temperature of a water bath to 25 ℃, and magnetically stirring for 30min to obtain a suspension;
s2, mixing the materials to obtain 100g K2Cr2O7Adding the mixture into the suspension obtained in the first step, adjusting the temperature of a water bath to 30 ℃, and continuously stirring for reaction for 1 hour;
s3, adding 5kg of ammonium persulfate into the suspension obtained in the second step of reaction, adjusting the temperature of a water bath to 10 ℃, and reacting for 5 min;
s4, after the reaction is finished, performing suction filtration and washing by using a glass fiber membrane until the filtrate is neutral, and drying the filter cake in a 60 ℃ drying oven for 8 hours to obtain the graphite nano bubble material;
s5, adding 500g of graphite nano-bubble material and 1kg of PVP into 15L water to obtain a dispersion, carrying out ultrasonic treatment for 4h in industrial-grade ultrasonic equipment (3000W), centrifuging the dispersion in a centrifuge at 6000rpm for 30min, removing precipitates, obtaining graphene nano-bubble material dispersion in an upper layer liquid, filtering the dispersion by using a 0.22 mu m filter membrane, washing the dispersion for multiple times by using water, and finally carrying out vacuum drying for 10h at 80 ℃ to obtain the graphene nano-bubble material.
Fig. 1 shows an SEM image of the intermediate graphite nanobubble material obtained in example 1, and it can be seen that the graphite surface contains a large number of bubbles.
Fig. 2 shows an SEM image of the graphene nanobubble material obtained in example 1, from which it can be seen that there are still bubbles on the graphene sheet, illustrating the formation of the graphene nanobubble material.
FIG. 3 shows the Raman spectrum of the graphene nanobubble material obtained in example 1, wherein 1350cm is observed-1Corresponding to peak D, 1580cm-1Corresponding to the G peak, 2728cm-1Corresponding to the 2D peak, ID/IGThe 2D peak shape is symmetrical, and the prepared graphene nano-bubble material is proved to have few defects.
Fig. 4 shows an XRD pattern of the graphene nanobubble material obtained in example 1, and it can be seen that 2 θ is 26.30 °, and the structure of the surface graphite is not destroyed in this process.
Example 2
A preparation method of a graphene nano-bubble material comprises the following steps:
s1, weighing 100g of expandable graphite, adding 1kg of concentrated sulfuric acid (98 wt%) and 8kg of perchloric acid, adjusting the temperature of a water bath to 25 ℃, and magnetically stirring for 30min to obtain a suspension;
s2, mixing 4g KMnO4And 16g K2Cr2O7Adding the mixture into the suspension obtained in the first step, adjusting the temperature of a water bath to 30 ℃, and continuously stirring for reaction for 1 hour;
s3, adding 8kg of ammonium persulfate into the suspension obtained in the second step of reaction, adjusting the temperature of a water bath to 10 ℃, and reacting for 5 min;
s4, after the reaction is finished, performing suction filtration and washing by using a glass fiber membrane until the filtrate is neutral, and drying the filter cake in a 60 ℃ drying oven for 8 hours to obtain the graphite nano bubble material;
s5, taking 10g of graphite nano-bubble material and 200g of sodium bicarbonate as raw materials and auxiliary agents for ball milling, adding 600g of ethanol into a planetary ball mill, and filling 2kg of zirconia grinding balls, wherein the ratio of the large balls: a middle ball: the mass ratio of the pellets was 3:4:3, so that the volume of the dispersion was 1/3. The rotation speed is set to be 240rpm, and the ball milling time is set to be 6 h. And (3) taking out the dispersion liquid after the ball milling is finished, performing filter pressing washing by using a 0.22 mu m filter membrane until the washing liquid is neutral, and redispersing the filter cake in water for freeze drying for 12 hours to obtain the graphene nano-bubble material.
Example 3
A preparation method of a graphene nano-bubble material comprises the following steps:
s1, weighing 10g of expandable graphite, adding 200g of concentrated sulfuric acid (98 wt%) and 50g of perchloric acid, adjusting the temperature of a water bath to 25 ℃, and magnetically stirring for 30min to obtain a suspension;
s2, mixing 2g KCIO3Adding the mixture into the suspension obtained in the first step, adjusting the temperature of a water bath to 30 ℃, and continuously stirring for reaction for 1 hour;
s3, 80g H2O2(20%) adding into the suspension obtained in the second step, adjusting the temperature of the water bath at 10 deg.C, and reacting for 5 min;
s4, after the reaction is finished, performing suction filtration and washing by using a glass fiber membrane until the filtrate is neutral, and drying the filter cake in a 60 ℃ drying oven for 8 hours to obtain the graphite nano bubble material;
s5, adding 5g of graphite nano-bubble material into 100g of NMP to obtain dispersion liquid, carrying out ultrasonic treatment for 1h in an ultrasonic cell crusher (900W), centrifuging the dispersion liquid in a centrifuge at 6000rpm for 30min, removing precipitates, obtaining graphene nano-bubble material dispersion liquid in supernatant liquid, filtering the dispersion liquid by using a 0.22 mu m filter membrane, washing for multiple times by using ethanol and water, and finally drying at 80 ℃ for 10h to obtain the graphene nano-bubble material.
Example 4
A preparation method of a graphene nano-bubble material comprises the following steps:
s1, weighing 100g of flake graphite, adding 2kg of concentrated sulfuric acid (98 wt%), adjusting the temperature of a water bath to 15 ℃, and magnetically stirring for 1 hour to obtain a suspension;
s2, adding 20g of potassium ferrate into the suspension obtained in the first step, adjusting the temperature of a water bath to 50 ℃, and continuously stirring for reaction for 3 hours;
s3, adding 1kg of ammonium persulfate into the suspension obtained in the second step of reaction, adjusting the temperature of the water bath to 20 ℃, and reacting for 3 min;
s4, after the reaction is finished, performing suction filtration and washing by using a glass fiber membrane until the filtrate is neutral, and drying the filter cake in a drying oven at 100 ℃ for 6 hours to obtain the graphite nano-bubble material;
s5, adding 50g of graphite nano-bubble material into 100g of NMP to obtain dispersion liquid, shearing and stirring for 30min at 6000rpm in a high-shear emulsification dispersion machine, centrifuging the dispersion liquid for 30min at 6000rpm in a centrifugal machine, removing precipitates, obtaining graphene nano-bubble material dispersion liquid in upper layer liquid, filtering the dispersion liquid by using a 0.22 mu m filter membrane, washing for multiple times by using ethanol and water, and finally drying for 10h at 80 ℃ to obtain the graphene nano-bubble material.
Example 5
A preparation method of a graphene nano-bubble material is different from embodiment 4 in that the mass of concentrated sulfuric acid in the embodiment is 11kg, the mass of potassium ferrate is 5g, the mass of ammonium persulfate is 400g, and the rest is the same as that in embodiment 4.
The mass ratio of each raw material in this example is out of the preferable range of the present invention.
Examples 6 to 8
A method for preparing a graphene nanobubble material, which is different from example 4 in that in examples 6 to 8, the reaction temperatures in step S1 are 0, 50 and 55 ℃, the reaction times are 4h, 10min and 5min, respectively, and the rest is the same as example 4.
The reaction temperature and reaction time in step S1 in example 8 are out of the preferable range of the present invention.
As can be seen from fig. 5, 6a to 6d, the effect of example 4 is superior to that of examples 5 to 8, and the experimental results of examples 6 and 7 are superior to that of example 8.
Examples 9 to 11
A method for preparing a graphene nanobubble material, which is different from example 4 in that in examples 9 to 11, the reaction temperatures in step S2 are 0, 60 and 65 ℃, the reaction times are 10h, 30min and 20min, respectively, and the rest is the same as example 4.
The reaction temperature and reaction time in step S2 in example 11 are out of the preferable range of the present invention.
As can be seen from fig. 5 and fig. 7a to 7c, the bubbles of example 4 are large and the lamella thickness is thick, the bubbles of example 9 are general and the lamella thickness is thick, the bubbles of example 10 are small and the lamella thickness is thick, the bubbles of example 11 are small and the lamella thickness is thin, and it can be seen that the effect of example 4 is better than that of examples 9 to 11, and the experimental results of examples 9 and 10 are better than that of example 11.
Examples 12 to 14
Different from the embodiment 4, in the embodiments 12 to 14, the reaction temperatures in the step S3 are 0, 40 and-5 ℃, the reaction times are 1h, 1min and 3h, respectively, and the rest is the same as the embodiment 4.
The reaction temperature and reaction time in step S3 in example 14 are out of the preferable range of the present invention.
As can be seen from fig. 5 and fig. 8a to 8c, the number of bubbles and the sheet thickness in example 4 are large, the number of bubbles and the sheet thickness in example 12 are small, the number of bubbles and the sheet thickness in example 13 are generally small, and the number of bubbles and the sheet thickness in example 14 are small, so that the effect of example 4 is better than those of examples 12 to 14, and the experimental results of examples 12 and 13 are better than those of example 14.
Examples 15 to 17
Different from the embodiment 4, in the embodiments 15 to 17, the drying temperatures in the step S4 are respectively 30 ℃, 120 ℃ and 28 ℃, the reaction times are respectively 12h, 3h and 24h, and the rest is the same as the embodiment 4.
The drying temperature and drying time in step S4 in example 17 are out of the preferable range of the present invention.
As can be seen from fig. 5 and fig. 9a to 9c, the number of bubbles and the sheet thickness in example 4 are large, the number of bubbles and the sheet thickness in example 15 are small, the number of bubbles and the sheet thickness in example 16 are small, and the number of bubbles in example 17 is particularly small, so that the effect of example 4 is better than that of examples 15 to 17, and the experimental results of examples 15 and 16 are better than that of example 17.
Comparative example 1
Different from the embodiment 1, the preparation method of the graphene nano bubble material does not comprise the step S1, and 1kg of crystalline flake graphite and 100g K are directly mixed in the step S22Cr2O7Mixing, adjusting the temperature of a water bath kettle to 30 ℃, continuously stirring and reacting for 1h, and the rest steps are the same as the example 1.
Comparative example 2
A preparation method of a graphene nano-bubble material is different from that of example 1 in that step S2 is not included in the comparative example, 5kg of ammonium persulfate is added into suspension obtained in the first step in step S3, the temperature of a water bath is adjusted to 10 ℃, the reaction is carried out for 5min, and the rest steps are the same as those of example 1.
Comparative example 3
Unlike example 1, in the present comparative example, steps S1 to S3 were replaced with: 1kg of flake graphite, 20kg of concentrated sulfuric acid (98 wt%), 10kg of concentrated nitric acid (67 wt%), and 100g K2Cr2O7And 5kg of ammonium persulfate were mixed together, and then the reaction was stirred at 25 ℃ for 1 hour, and steps S4 and S5 were the same as in example 1.
The intermediate products obtained in comparative examples 1 to 3 were also observed under an electron microscope, and as a result, it was found that: in comparative example 1, graphite lumps were present due to the lack of an oxidizing acid system. In the absence of the intercalant in comparative example 2, the graphite was weakly intercalated and the edges were somewhat curled as shown in the electron microscope. In the comparative example 3, all the substances are mixed together, the graphite directly reacts without oxidation intercalation, and no bubbles appear on the surface of the graphite.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. A preparation method of a graphene nano-bubble material is characterized by comprising the following steps:
(a) heating and reacting a graphite raw material with oxidizing acid;
(b) heating and reacting a product obtained by the reaction in the step (a) with an intercalation agent;
(c) heating and reacting the product obtained in the step (b) with an expanding agent, and carrying out solid-liquid separation after reaction to obtain a graphite nano bubble material;
(d) and carrying out mechanical force treatment on the graphite nano bubble material to obtain the graphene nano bubble material.
2. The method of claim 1, wherein the graphite starting material comprises at least one of flake graphite, expandable graphite, or expanded graphite.
3. The production method according to claim 1, wherein the oxidizing acid comprises at least one of concentrated sulfuric acid, concentrated nitric acid, perchloric acid, hypochloric acid, or permanganic acid;
preferably, the intercalant comprises K2Cr2O7、H2O2、KMnO4、(NH4)2S2O8、O3、CrO3Or K2FeO4At least one of;
preferably, the swelling agent comprises (NH)4)2C2O4、H2O2、(NH4)2S2O8、H2C2O4、NH4HCO3Or NH4NO3At least one of;
preferably, the intercalant and the expansion agent are different.
4. The preparation method according to claim 1, wherein the mass ratio of the graphite raw material, the oxidizing acid, the intercalating agent and the expanding agent is 1: (18-108): (0.1-1): (5-60), preferably 1: (45-55): (0.2-0.8): (5-20), more preferably 1: 50: 0.5: 10.
5. the method according to claim 1, wherein in the step (a), the heating reaction temperature is 0-50 ℃ and the reaction time is 10min-4 h;
preferably, in the step (b), the heating reaction temperature is 0-60 ℃, and the reaction time is 30min-10 h;
preferably, in step (c), the heating reaction temperature is 0-40 ℃ and the reaction time is 1min-1 h.
6. The preparation method according to claim 1, characterized by further comprising the steps of washing and drying in sequence after the solid-liquid separation, and then obtaining the graphite nanobubble material;
preferably, the drying temperature is 30-120 ℃ and the drying time is 3-12 h.
7. The method according to any one of claims 1 to 6, wherein the mechanical treatment is carried out by at least one of an ultrasonic method, a ball milling method, a high shear emulsifying dispersion method, a high pressure homogenization method, a jet milling method, a high gravity rotation method, a supercritical fluid method, and a microfluidization method.
8. The graphene nano-bubble material obtained by the preparation method of any one of claims 1 to 7.
9. Use of the graphene nanobubble material of claim 8 in the preparation of adsorbents, catalysts, optical materials or energy storage materials.
10. An adsorbent, catalyst, optical material or energy storage material comprising the graphene nanobubble material of claim 8.
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| CN104058396A (en) * | 2014-07-14 | 2014-09-24 | 复旦大学 | Method for preparing large-size high-quality graphene with controllable number of layers |
| CN104803380A (en) * | 2015-05-12 | 2015-07-29 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene |
| CN105293476A (en) * | 2015-11-16 | 2016-02-03 | 复旦大学 | Preparation method of large-size graphene oxide or graphene |
| CN106744883A (en) * | 2017-01-05 | 2017-05-31 | 中山科普斯特电源技术有限公司 | The preparation method of Graphene |
| CN107973293A (en) * | 2017-12-18 | 2018-05-01 | 昂星新型碳材料常州有限公司 | The preparation method and graphene of graphene |
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| CN113083037A (en) * | 2021-03-31 | 2021-07-09 | 天津大学 | Preparation method of graphene oxide water treatment membrane capable of generating surface nanobubbles in situ |
| CN113083037B (en) * | 2021-03-31 | 2022-07-12 | 天津大学 | Preparation method of graphene oxide water treatment membrane capable of generating surface nanobubbles in situ |
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