CN113941120B - Digestion method of graphene material - Google Patents
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Abstract
本发明属于石墨材料分析技术领域，具体涉及一种石墨烯材料的消解方法。本发明的消解方法中，包括：（1）石墨烯的氧化：将石墨烯氧化，以形成氧化石墨烯；（2）氧化石墨烯的改性处理：在氧化石墨烯共轭区引入氨基；（3）消解处理：将改性后的氧化石墨烯和氢氟酸混合后，于温度为170‑200℃，加压至压力为0.20‑0.32MPa条件下，保压20‑60min后，泄压至常压，于常压下反应10‑60min，如此加压泄压循环3‑5次，出料。其中，所述泄压至常压为：于10‑30s内泄压至常压。本发明可以高效完成对石墨烯的消解处理，避免石墨烯的残留影响测试结果准确性。The invention belongs to the technical field of graphite material analysis, and in particular relates to a method for digestion of graphene materials. The digestion method of the present invention includes: (1) oxidation of graphene: oxidizing graphene to form graphene oxide; (2) modification treatment of graphene oxide: introducing amino groups into the conjugated region of graphene oxide; ( 3) Digestion treatment: after mixing the modified graphene oxide and hydrofluoric acid, at a temperature of 170-200°C, pressurized to a pressure of 0.20-0.32MPa, after maintaining the pressure for 20-60min, release the pressure to Under normal pressure, react for 10-60min under normal pressure, and cycle 3-5 times of pressurizing and depressurizing, and discharging. Wherein, the pressure relief to normal pressure is: the pressure relief to normal pressure within 10-30s. The invention can efficiently complete the digestion treatment of the graphene, and avoid the residual of the graphene from affecting the accuracy of the test result.
Description
Technical Field
The invention belongs to the technical field of graphite material analysis. And more particularly, to a digestion method of graphene materials.
Background
Graphene (GNs) is a two-dimensional planar material formed by orderly arranging and combining carbon atoms, and is mainly formed by the hybridization effect reaction of the carbon atoms. In the hybridization effect of carbon atoms, the carbon atoms undergo a series of reactions to gradually change into C = C double bonds and C — C single bonds, and partially form C — H bonds. In addition, the P electrons in the carbon atoms are accumulated, and pi electrons that can move freely are formed in the vertical plane. The structure enables graphene to have very stable stability and extremely high hydrophilicity, and meanwhile, the graphene has aromaticity, oxidizability and reducibility which are different from other substances.
Graphene is expected by scientists in the world as one of the most promising new materials. The application of graphene is very wide, and the body image of the substance can be seen in various scientific and technological advanced research fields including catalysis, energy storage, adsorption and sensing, and plays a key role in the research field. However, while being hopeful, the graphene, a new material full of the future beauty vision of human beings, releases huge 'maliciousness' when being applied, and has no small harm to human bodies and the environment. How to efficiently digest the stable substance graphene becomes one of the major bottlenecks that restrict the application of the substance graphene.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects and shortcomings of stable structure and difficult digestion of the existing graphene material and providing a digestion method of the graphene material.
The invention aims to provide a digestion method of a graphene material.
The above purpose of the invention is realized by the following technical scheme:
a digestion method of a graphene material comprises the following specific digestion steps:
(1) oxidation of graphene:
oxidizing graphene to form graphene oxide;
(2) modification treatment of graphene oxide:
introducing amino groups into the graphene oxide conjugated region;
(3) digestion treatment:
mixing the modified graphene oxide and hydrofluoric acid, pressurizing to 0.20-0.32MPa at the temperature of 170-200 ℃, maintaining the pressure for 20-60min, then relieving the pressure to normal pressure, reacting for 10-60min at normal pressure, and performing pressurization and pressure relief circulation for 3-5 times, and discharging.
According to the technical scheme, firstly, graphene is oxidized, amino is introduced into a hydrophobic conjugate zone of the oxidized graphene, then, during digestion, hydrogen ions of hydrofluoric acid can protonate the amino in the conjugate zone, the process occurs, the original hydrophobic conjugate zone is changed into hydrophilic property, the hydrofluoric acid is easier to enter, meanwhile, due to the fact that the hydrogen ions have the same positive charge, due to the principle that the two adjacent graphene oxide lamellar structures are detached from each other in the same polarity, the interlayer distance is effectively enlarged, more hydrofluoric acid is easier to enter the inner structure of the graphene oxide, and stripping and digestion of the graphene oxide are accelerated.
In addition, according to the technical scheme, in the digestion process, pressurization treatment is performed firstly, so that hydrofluoric acid permeates into the graphene oxide layers, then pressure relief treatment is performed, the hydrofluoric acid between the layers is gasified quickly, the graphene oxide lamellar structure is stripped quickly by pressure generated by gasification, and in the subsequent pressurization and pressure relief circulation process, the hydrofluoric acid permeates quickly, so that the graphene oxide inside is further digested, and the reaction process and the reaction effect are accelerated.
Further, the graphene is oxidized by: adding graphene into concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, stirring and reacting at the temperature of 30-40 ℃, filtering, washing and drying to obtain the graphene oxide.
According to the technical scheme, the concentrated sulfuric acid is adopted to oxidize the graphene, so that an epoxy group required by subsequent reaction can be formed in a conjugated region in a graphene molecular structure, and carbon-containing impurities in the graphene material can be removed by carbonization.
Further, the modification treatment of the graphene oxide is as follows: mixing graphene oxide and a sodium azide solution for reaction, filtering, washing and drying to obtain pretreated graphene oxide, dispersing the pretreated graphene oxide in tetrahydrofuran, adding lithium aluminum hydride, performing reduction reaction, filtering and drying to obtain amino-introduced graphene oxide.
Further, the pressure relief to normal pressure is as follows: and (5) releasing the pressure to the normal pressure within 10-30 s.
Above-mentioned technical scheme further changes the pressure release rate among the pressure release process for in the short time, pressure reduces fast, and from this, the liquid between the graphite alkene layer can take place fast gasification, thereby arouses the disintegration and the peeling off of graphite alkene lamellar structure, promotes the efficiency and the effect of clearing up.
Further, the digestion processing further includes: adding an emulsifier with the mass of 1-3% of the hydrofluoric acid into the hydrofluoric acid.
Further, the emulsifier is any one of sodium lignosulfonate, sodium dodecyl benzene sulfonate, emulsifier OP-10 and span-80.
Above-mentioned technical scheme further introduces the emulsifier, so, at pressurization and pressure release in-process that relapse, utilize the bubbling effect that pressure variation produced, can form a large amount of foams in the system, the production of foam can be so that the monolithic layer oxidation graphite alkene after peeling off is fixed by the liquid film adsorption of foam, avoids taking place the reunion again to make subsequent reaction of clearing up go on under the foam environment of emulsification, so, can promote the area of contact of hydrogen fluoride and oxidation graphite alkene, promote and clear up efficiency.
Further, after the modification treatment of the graphene oxide and before the digestion treatment, the modified graphene oxide is dispersed in water and spray-granulated.
Further, the particle size distribution of the spray-granulated particles is 10 to 50 μm.
According to the technical scheme, spray granulation is utilized, and the particle size of granulation is controlled, so that the surface energy of graphene oxide can be changed by utilizing the spray granulation, and the graphene oxide can be rapidly dispersed in a digested solution system more easily; and, after spray granulation, the even lamellar structure of graphite oxide can obtain certain degree destruction, changes into the structure that the edge is curled into, so, at the edge, hydrofluoric acid can be more easily to graphite oxide's interlaminar diffusion infiltration for the speed of dispelling.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
Oxidation of graphene:
according to the mass ratio of 1: 5, adding graphene into concentrated sulfuric acid with the mass fraction of 98%, adding sodium nitrate with the mass fraction of 5% of the concentrated sulfuric acid and potassium permanganate with the mass fraction of 5% of the concentrated sulfuric acid, stirring and reacting at the constant temperature of 30 ℃ and the rotation speed of 200r/min for 2 hours, filtering, collecting a filter cake, washing the obtained filter cake to be neutral, drying in an oven at the temperature of 110 ℃ to constant weight, and discharging to obtain graphene oxide;
modification treatment of graphene oxide:
mixing graphene oxide and a sodium azide solution with the mass fraction of 10% according to the mass ratio of 1: 5, after mixing, stirring at a constant temperature of 65 ℃ and a stirring speed of 300r/min for reaction for 3 hours, filtering, washing and drying to obtain pretreated graphene oxide, dispersing the pretreated graphene oxide in tetrahydrofuran, adding lithium aluminum hydride accounting for 3% of the mass of the pretreated graphene oxide, carrying out reduction reaction for 2 hours at a temperature of 65 ℃ and a stirring speed of 300r/min, filtering and drying to obtain amino-introduced graphene oxide;
spray granulation:
dispersing graphene oxide introduced with amino into water, controlling the addition of the graphene oxide to be 10% of the mass of the water, then carrying out spray granulation under the conditions that the air inlet temperature is 130 ℃ and the air outlet temperature is 80 ℃, and regulating and controlling the particle size distribution of granulated particles to be 10-50 mu m to obtain graphene oxide particles;
digestion treatment:
mixing oxidized graphene particles and 40% hydrofluoric acid according to a mass ratio of 1: 8, mixing, pouring into a polytetrafluoroethylene-lined stainless steel reaction kettle, adding an emulsifier with the mass of 1% of hydrofluoric acid, pressurizing to 0.20MPa at the temperature of 170 ℃, maintaining the pressure for 20min, then releasing the pressure to normal pressure within 10s, reacting for 10min at normal pressure, so pressurizing and releasing the pressure for 3 times, and discharging to finish the digestion treatment of the graphene; the emulsifier is selected from sodium lignosulfonate.
Example 2
Oxidation of graphene:
according to the mass ratio of 1: 8, adding graphene into concentrated sulfuric acid with the mass fraction of 98%, adding sodium nitrate with the mass fraction of 6% of the concentrated sulfuric acid and potassium permanganate with the mass fraction of 7% of the concentrated sulfuric acid, stirring and reacting for 3 hours at the constant temperature under the conditions that the temperature is 35 ℃ and the rotating speed is 250r/min, filtering, collecting a filter cake, washing the obtained filter cake to be neutral, drying in an oven at the temperature of 115 ℃ to constant weight, and discharging to obtain graphene oxide;
modification treatment of graphene oxide:
mixing graphene oxide and a sodium azide solution with the mass fraction of 12% in a mass ratio of 1: 8, after mixing, stirring at a constant temperature of 70 ℃ and a stirring speed of 400r/min for reaction for 4 hours, filtering, washing and drying to obtain pretreated graphene oxide, dispersing the pretreated graphene oxide in tetrahydrofuran, adding lithium aluminum hydride accounting for 5% of the mass of the pretreated graphene oxide, carrying out reduction reaction for 3 hours at a temperature of 68 ℃ and a stirring speed of 400r/min, filtering and drying to obtain amino-introduced graphene oxide;
spray granulation:
dispersing graphene oxide introduced with amino into water, controlling the addition of the graphene oxide to be 13% of the mass of the water, then carrying out spray granulation under the conditions that the air inlet temperature is 135 ℃ and the air outlet temperature is 85 ℃, and regulating and controlling the particle size distribution of granulated particles to be 20-50 mu m to obtain graphene oxide particles;
digestion treatment:
mixing oxidized graphene particles and 45% hydrofluoric acid according to a mass ratio of 1: 9, mixing, pouring into a polytetrafluoroethylene-lined stainless steel reaction kettle, adding an emulsifier with the mass of 2% of hydrofluoric acid, pressurizing to 0.26MPa at the temperature of 190 ℃, maintaining the pressure for 40min, then releasing the pressure to normal pressure within 20s, reacting for 30min at normal pressure, so pressurizing and releasing the pressure for circulation for 4 times, and discharging to finish the digestion treatment of the graphene; the emulsifier is selected from sodium dodecyl benzene sulfonate.
Example 3
Oxidation of graphene:
according to the mass ratio of 1: 10, adding graphene into concentrated sulfuric acid with the mass fraction of 98%, adding sodium nitrate with the mass fraction of 10% of the concentrated sulfuric acid and potassium permanganate with the mass fraction of 10% of the concentrated sulfuric acid, stirring and reacting for 4 hours at a constant temperature under the conditions that the temperature is 40 ℃ and the rotating speed is 300r/min, filtering, collecting a filter cake, washing the obtained filter cake to be neutral, drying in an oven at the temperature of 120 ℃ to constant weight, and discharging to obtain graphene oxide;
modification treatment of graphene oxide:
mixing graphene oxide and a sodium azide solution with the mass fraction of 15% according to the mass ratio of 1: 10, after mixing, stirring and reacting at a constant temperature of 75 ℃ and a stirring speed of 500r/min for 5 hours, filtering, washing and drying to obtain pretreated graphene oxide, dispersing the pretreated graphene oxide in tetrahydrofuran, adding lithium aluminum hydride accounting for 8% of the mass of the pretreated graphene oxide, reducing and reacting at a temperature of 75 ℃ and a stirring speed of 500r/min for 4 hours, filtering and drying to obtain amino-introduced graphene oxide;
spray granulation:
dispersing graphene oxide introduced with amino into water, controlling the addition of the graphene oxide to be 15% of the mass of the water, then carrying out spray granulation under the conditions that the air inlet temperature is 140 ℃ and the air outlet temperature is 90 ℃, and regulating and controlling the particle size distribution of granulated particles to be 10-30 mu m to obtain graphene oxide particles;
digestion treatment:
mixing oxidized graphene particles and 48% by mass of hydrofluoric acid according to a mass ratio of 1: 10 mixing and pouring the mixture into a polytetrafluoroethylene-lined stainless steel reaction kettle, adding an emulsifier with the mass of 3% of hydrofluoric acid, pressurizing at the temperature of 200 ℃ to the pressure of 0.32MPa, maintaining the pressure for 60min, then releasing the pressure to the normal pressure within 30s, reacting for 60min at the normal pressure, so pressurizing and releasing the pressure for 5 times, and discharging to finish the digestion treatment of the graphene; the emulsifier is selected from emulsifier OP-10.
Example 4
This example differs from example 1 in that: after the modification treatment of the graphene oxide, the spray granulation treatment is not performed, and the digestion treatment is directly performed, and the rest conditions are kept unchanged.
Example 5
This example differs from example 1 in that: in the digestion treatment process, when the pressure is released, the pressure is released to normal pressure within 1min, and the rest conditions are kept unchanged.
Example 6
This example differs from example 1 in that: no emulsifier was added and the remaining conditions were kept constant.
Comparative example 1
Oxidation of graphene:
according to the mass ratio of 1: 5, adding graphene into concentrated sulfuric acid with the mass fraction of 98%, adding sodium nitrate with the mass fraction of 5% of the concentrated sulfuric acid and potassium permanganate with the mass fraction of 5% of the concentrated sulfuric acid, stirring and reacting at the constant temperature of 30 ℃ and the rotation speed of 200r/min for 2 hours, filtering, collecting a filter cake, washing the obtained filter cake to be neutral, drying in an oven at the temperature of 110 ℃ to constant weight, and discharging to obtain graphene oxide;
modification treatment of graphene oxide:
mixing graphene oxide and a sodium azide solution with the mass fraction of 10% according to the mass ratio of 1: 5, after mixing, stirring at a constant temperature of 65 ℃ and a stirring speed of 300r/min for reaction for 3 hours, filtering, washing and drying to obtain pretreated graphene oxide, dispersing the pretreated graphene oxide in tetrahydrofuran, adding lithium aluminum hydride accounting for 3% of the mass of the pretreated graphene oxide, carrying out reduction reaction for 2 hours at a temperature of 65 ℃ and a stirring speed of 300r/min, filtering and drying to obtain amino-introduced graphene oxide;
spray granulation:
dispersing graphene oxide introduced with amino into water, controlling the addition of the graphene oxide to be 10% of the mass of the water, then carrying out spray granulation under the conditions that the air inlet temperature is 130 ℃ and the air outlet temperature is 80 ℃, and regulating and controlling the particle size distribution of granulated particles to be 10-50 mu m to obtain graphene oxide particles;
digestion treatment:
mixing oxidized graphene particles and 40% hydrofluoric acid according to a mass ratio of 1: 8, mixing, pouring into a polytetrafluoroethylene-lined stainless steel reaction kettle, adding an emulsifier with the mass of 1% of hydrofluoric acid, pressurizing at the temperature of 170 ℃ to the pressure of 0.20MPa, maintaining the pressure for 20min, and discharging to finish the digestion treatment of the graphene; the emulsifier is selected from sodium lignosulfonate.
Comparative example 2
Oxidation of graphene:
according to the mass ratio of 1: 5, adding graphene into concentrated sulfuric acid with the mass fraction of 98%, adding sodium nitrate with the mass fraction of 5% of the concentrated sulfuric acid and potassium permanganate with the mass fraction of 5% of the concentrated sulfuric acid, stirring and reacting at the constant temperature of 30 ℃ and the rotation speed of 200r/min for 2 hours, filtering, collecting a filter cake, washing the obtained filter cake to be neutral, drying in an oven at the temperature of 110 ℃ to constant weight, and discharging to obtain graphene oxide;
spray granulation:
dispersing graphene oxide in water, controlling the addition of the graphene oxide to be 10% of the mass of the water, then carrying out spray granulation under the conditions that the air inlet temperature is 130 ℃ and the air outlet temperature is 80 ℃, and regulating and controlling the particle size distribution of granulated particles to be 10-50 mu m to obtain graphene oxide particles;
digestion treatment:
mixing oxidized graphene particles and 40% hydrofluoric acid according to a mass ratio of 1: 8, mixing, pouring into a polytetrafluoroethylene-lined stainless steel reaction kettle, adding an emulsifier with the mass of 1% of hydrofluoric acid, pressurizing to 0.20MPa at the temperature of 170 ℃, maintaining the pressure for 20min, then releasing the pressure to normal pressure within 10s, reacting for 10min at normal pressure, so pressurizing and releasing the pressure for 3 times, and discharging to finish the digestion treatment of the graphene; the emulsifier is selected from sodium lignosulfonate.
The digestion solutions obtained in examples 1 to 6 and comparative examples 1 to 2 were subjected to observation tests, and the specific test results are shown in table 1.
Table 1:
as can be seen from the test results in Table 1, clear and transparent digestion solution which is completely digested can be effectively obtained by digesting the graphene by adopting the technical scheme of the invention.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. The digestion method of the graphene material is characterized by comprising the following specific digestion steps:
(1) oxidation of graphene:
adding graphene into concentrated sulfuric acid, adding sodium nitrate and potassium permanganate, stirring and reacting at the temperature of 30-40 ℃, filtering, washing and drying to obtain graphene oxide;
(2) modification treatment of graphene oxide:
mixing graphene oxide and a sodium azide solution for reaction, filtering, washing and drying to obtain pretreated graphene oxide, dispersing the pretreated graphene oxide in tetrahydrofuran, adding lithium aluminum hydride, performing reduction reaction, filtering and drying to obtain amino-introduced graphene oxide;
(3) digestion treatment:
mixing the modified graphene oxide and hydrofluoric acid, pressurizing to 0.20-0.32MPa at the temperature of 170-200 ℃, maintaining the pressure for 20-60min, then relieving the pressure to normal pressure within 10-30s, reacting for 10-60min at normal pressure, and performing pressurization and pressure relief circulation for 3-5 times to discharge;
the digestion treatment further comprises the following steps: adding an emulsifier with the mass of 1-3% of hydrofluoric acid into the hydrofluoric acid; the emulsifier is selected from any one of sodium lignosulphonate, sodium dodecyl benzene sulfonate, emulsifier OP-10 and span-80.
2. The digestion method for graphene materials according to claim 1, wherein after the modification treatment of the graphene oxide and before the digestion treatment, the modified graphene oxide is dispersed in water and spray granulated.
3. The digestion method for graphene materials according to claim 2, wherein the particle size distribution of the spray granulation is 10-50 μm.
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