CN108568218B - Preparation method of porous graphene membrane and application of porous graphene membrane in aspect of carbon dioxide capture - Google Patents
Preparation method of porous graphene membrane and application of porous graphene membrane in aspect of carbon dioxide capture Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 79
- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 23
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 24
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- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000009388 chemical precipitation Methods 0.000 claims abstract description 7
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 14
- 239000003546 flue gas Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000001064 degrader Substances 0.000 claims description 3
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 20
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 229910002484 Ce0.9Gd0.1O1.95 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0053—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/006—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes by elimination of segments of the precursor, e.g. nucleation-track membranes, lithography or laser methods
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Engineering & Computer Science (AREA)
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- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a porous graphene membrane and application of the porous graphene membrane in carbon dioxide capture, and belongs to the field of film preparation. The preparation method of the porous graphene film comprises the following steps of 1: preparation of porous alpha-Al by colloid filtration method2O3A substrate; step 2: preparation of Gd-doped CeO by ultrasonic chemical precipitation2The nanoparticle sol precursor of (a); and step 3: by dipping and pulling method on porous alpha-Al2O3Depositing a layer of Ce on the substrate0.9Gd0.1O1.95Preparing a GDC buffer layer by a precursor film through drying and rapid annealing process; and 4, step 4: coating graphene oxide suspension liquid with different concentrations on alpha-Al by using spin coating process2O3Drying the supported GDC buffer layer in an oven to obtain a graphene oxide membrane; and 5: by means of H2And (3) performing an atmosphere thermal reduction process to prepare the porous graphene film. The porous graphene membrane prepared by the invention has the advantages of good separation performance, good mechanical property and chemical stability, simple and convenient preparation process and low manufacturing cost, can realize the mass production of products, and has good marketization prospect.
Description
Technical Field
The invention belongs to the field of film preparation, and particularly relates to a preparation method of a porous graphene film and application of the porous graphene film in carbon dioxide flue gas separation.
Background
In recent years, with the rapid development of industry, the consumption of fossil fuel is increased sharply, and flue gas generated after the fuel is combusted contains 13 vol% of carbon dioxide (CO)2)、17vol％H2O、67vol％N2、2vol％O2Iso-gas to make CO in the atmosphere2The content increases year by year. CO 22As a main greenhouse gas, it has severe influence on the climate, resulting in severe environmental problems such as extreme weather and rising sea levelThe normal production and life of human beings are seriously threatened. For this purpose, CO is reduced2The discharge of (2) is imperative. However, at present, for CO2Flue gas capture technology has presented several challenges: (1) flue gas CO2The air pressure is lower, 1 atm; (2) CO in flue gas2Is relatively low, typically 13 vol%; (3) the size (kinetic diameter) of the various gas molecules varies little. All of these factors will result in reduced efficiency and increased cost of current separation techniques.
At present, CO2The collection method (2) is mainly an absorption method, an adsorption method, a membrane separation method, or the like. From the technical point of energy conservation and emission reduction, the membrane separation technology is considered to be CO with great application potential due to the unique advantages of small energy consumption, high efficiency and the like2A trapping separation technique. Existing polymer-based membranes have been extensively studied, but due to the strong trade-off relationship between the two main parameters, permeability and selectivity, separation membranes based on the properties of such materials have upper separation limits (upper limits). Many inorganic membrane materials (e.g., carbon and zeolites) have been found to overcome the upper separation limits of polymeric membranes, exhibit excellent separation performance, but it is often difficult to produce large-scale, defect-free membranes.
Graphene is the most popular two-dimensional new material in the field of nano carbon materials, high permeability of the membrane is easily realized due to the fact that the thickness of the graphene is smaller than 1nm, and appropriate pores (the size is between the sizes of two gas molecules, and the molecular dynamics diameter CO is the same as that of the two gas molecules) are formed in the graphene membrane layer by removing one carbon atom2：～0.33nm，N2: 0.36nm) and thus available for CO2High efficiency of trapping.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method which is simple and convenient in process, low in manufacturing cost and suitable for industrial production, develops a porous graphene membrane with high permeability and high selectivity, and realizes the purpose of realizing the low-concentration CO2To CO in flue gas2The effective trapping of (2).
In order to solve the technical problems, the invention provides the following technical scheme:
in one aspect, the present invention provides a method for preparing a porous graphene film, comprising:
step 1: preparation of porous alpha-Al by colloid filtration method2O3A substrate;
step 2: preparation of Gd-doped CeO by ultrasonic chemical precipitation2The nanoparticle sol precursor of (a);
and step 3: in porous alpha-Al2O3Depositing a layer of Ce on the substrate0.9Gd0.1O1.95(GDC) precursor film, drying and rapid annealing process to obtain GDC buffer layer;
and 4, step 4: coating graphene oxide suspension liquid with different concentrations on alpha-Al by using spin coating process2O3Drying the supported GDC buffer layer in an oven to obtain a graphene oxide membrane;
and 5: by means of H2And (3) removing oxygen-containing functional groups on the graphene oxide by an atmosphere thermal reduction process, so as to introduce pores into the graphene skeleton, and preparing the porous graphene film.
Further, the specific steps of step 1 are as follows:
11) alpha-Al having an average particle diameter of 300nm2O3Dispersing the powder in an aqueous solution, and stabilizing with nitric acid having a pH of 2;
12) stabilizing the alpha-Al2O3Obtaining a green body by adopting a vacuum filtration technology;
13) drying the green embryo in air for 24 h;
14) and (3) placing the dried green blank in a muffle furnace, and sintering for 10 hours at 950 ℃ in an air atmosphere to obtain a uniform disc-shaped ceramic matrix with a defect-free surface.
Further, in the step 14), the heating rate and the cooling rate of the muffle furnace are both 2 ℃/min.
Further, the step 2 comprises the following specific steps;
21) weighing ammonium ceric Nitrate (NH) according to the molar ratio of Ce to Gd of 0.9:0.14)2Ce(NO3)6And gadolinium nitrate Gd (NO)3)3·6H2O in a beakerAdding deionized water, and stirring to dissolve uniformly;
22) putting the mixed solution into an ultrasonic degrader, carrying out 55Watts ultrasonic treatment to uniformly dissolve the solution, and dropwise adding 25wt% of TMAOH solution while carrying out ultrasonic treatment to generate GDC dispersed particles;
23) weighing a certain amount of N-diglycine, and adding the N-diglycine into the dispersion liquid to stabilize the dispersion liquid; wherein the molar ratio of the N-diglycine to the GDC is 0.05;
24) and (3) carrying out ultrasonic treatment on the stable dispersion liquid for 5min under the condition of 55Watts to synthesize stable GDC precursor dispersion liquid.
Furthermore, in the step 3, a dipping and pulling method is used for dipping and pulling the porous alpha-Al2O3Deposition of Ce on the substrate0.9Gd0.1O1.95(GDC) precursor film;
the drying temperature is 110 ℃ for 1 h; the rapid annealing process is to rapidly cool the temperature from 600 ℃ to room temperature within 3 min.
Further, in the step 1, the porous alpha-Al2O3The porosity of the matrix is 25-35%, the thickness is 2-3 mm, the diameter is 42.5 mm, the size of the pores is-100 nm, the size of the surface pores is-40 nm, and the surface roughness is-30 nm. Because the alumina matrix is prepared by adopting a colloid filtration method, under the action of gravity, large particles in a suspension liquid are inevitably deposited at the bottom, and small particles are deposited on the surface of the matrix, so that the pore size of the surface of the matrix is smaller.
Further, in the step 2, Gd is doped with CeO2The doping amount of Gd in the nanoparticle sol precursor is 6-8.5 wt%.
Further, in the step 4, the drying temperature is 80-110 ℃.
Further, in the step 5, the H2The temperature of the atmosphere thermal reduction process is 300 ℃, and the reaction lasts for 1 h.
On the other hand, the invention also provides an application of the porous graphene membrane in the aspect of carbon dioxide capture, and the porous graphene membrane prepared by the preparation method of the porous graphene membrane is used for capturing carbon dioxide in flue gas.
The present invention provides a single-layer porous graphene membrane with high permeability and high selectivity, porous alpha-Al with high gas permeability2O3As a matrix, Ce0.9Gd0.1O1.95And preparing the porous graphene separation membrane supported by the ceramic matrix by using the graphene oxide as a precursor and adopting a dip-coating method and a spin-coating process.
The invention provides a preparation method of a porous graphene film and application of the porous graphene film in the aspect of carbon dioxide capture, and the porous graphene film has the following beneficial effects:
1) the separation performance is good, the graphene is taken as a single-layer carbon atom membrane material, the upper separation limit of a polymer membrane can be overcome, and the CO separation is realized2The high flux and the high selectivity of the gas are captured, and the separation of other different gases can be realized by controlling different pore sizes;
2) the invention has good mechanical property and chemical stability, takes ceramic as a matrix, and has good physical and chemical properties of stable size, temperature resistance, pressure resistance and the like compared with a polymer film and a polymer matrix film;
3) compared with the direct synthesis preparation of graphene, the chemical vapor deposition method requires multiple processes such as copper catalysis and film transfer, the technical route is simple and convenient in process and low in manufacturing cost, can realize the mass production of products, and has good marketization prospect.
4) The porous graphene membrane prepared by the invention is mainly applied to carbon dioxide capture in low-concentration carbon dioxide flue gas.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Materials, reagents and the like used in the following examples are commercially available.
The invention provides a preparation method of a porous graphene film and carbon dioxide capture, and the specific material dosage and experimental process are shown in the following examples.
Example 1:
a method of preparing a holey graphene membrane, comprising:
step 1: preparation of porous alpha-Al by colloid filtration method2O3Matrix:
11) alpha-Al having an average particle diameter of 300nm2O3Dispersing the powder in an aqueous solution, and stabilizing with nitric acid having a pH of 2;
12) stabilizing the alpha-Al2O3Obtaining a green body by adopting a vacuum filtration technology;
13) drying the green embryo in air for 24 h;
14) and (3) placing the dried green blank in a muffle furnace, sintering for 10 hours at 950 ℃ in an air atmosphere to prepare a uniform disc-shaped ceramic matrix with a defect-free surface, wherein the heating and cooling rates of the muffle furnace are both 2 ℃/min.
The resulting porous alpha-Al2O3The porosity of the matrix is 35 percent, the thickness is 2 millimeters, the diameter is 42.5 millimeters, the size of the pore is 100nm, the size of the surface pore is 40nm, and the surface roughness is 30 nm;
step 2: preparation of Gd-doped CeO by ultrasonic chemical precipitation2Of the nanoparticle sol precursor
21) Weighing ammonium ceric Nitrate (NH) according to the molar ratio of Ce to Gd of 0.9:0.14)2Ce(NO3)6And gadolinium nitrate Gd (NO)3)3·6H2Adding deionized water into a beaker, and stirring to dissolve the mixture uniformly;
22) putting the mixed solution into an ultrasonic degrader, carrying out 55Watts ultrasonic treatment to uniformly dissolve the solution, and dropwise adding 25wt% of TMAOH solution while carrying out ultrasonic treatment to generate GDC dispersed particles;
23) weighing a certain amount of N-diglycine, and adding the N-diglycine into the dispersion liquid to stabilize the dispersion liquid; wherein the molar ratio of the N-diglycine to the GDC is 0.05;
24) and (3) carrying out ultrasonic treatment on the stable dispersion liquid for 5min under the condition of 55Watts to synthesize stable GDC precursor dispersion liquid.
And step 3: then depositing a layer of Ce on the alumina substrate by using a dip-coating method0.9Gd0.1O1.95(GDC) precursor film is dried for 1h at 110 ℃, then heated to 600 ℃, and then rapidly cooled to room temperature within 3min, so as to improve the bonding strength between the graphene film layer and the substrate.
And 4, step 4: coating graphene oxide suspension with concentration of 2mg/mL on alpha-Al by using spin coating process2O3Drying the graphene oxide membrane in an oven at 110 ℃ on the supported GDC buffer layer;
and 5: by means of H2And (3) removing functional groups such as oxygen atoms, hydroxyl groups or carboxyl groups on the graphene oxide by an atmosphere thermal reduction process, so as to introduce pores into the graphene skeleton and prepare the porous graphene film.
The membrane material prepared by the process has a gas separation coefficient of-1 measured in a flue gas atmosphere, which is higher than a Knudsen (Knudsen) diffusion mechanism, and CO2Has a very low gas passage rate of about 2X 10-10mol/(m2·s·Pa)。
Example 2:
a method of preparing a holey graphene membrane, comprising:
step 1: preparation of porous alpha-Al by colloid filtration method2O3Matrix: the concrete steps refer to example 1;
step 2: preparation of 8.5 wt% Gd-doped CeO by ultrasonic chemical precipitation2The specific steps of the nanoparticle sol precursor of (1) are as described in example 1;
and step 3: then depositing a layer of Ce on the alumina substrate by using a dip-coating method0.9Gd0.1O1.95(GDC) precursor film, drying and rapid annealing process are carried out to prepare GDC buffer layer so as to improve the performance of graphene film layer and substrateThe specific procedure is as in example 1;
and 4, step 4: coating graphene oxide suspension with concentration of 1mg/mL on alpha-Al by using spin coating process2O3Drying the graphene oxide membrane in an oven at 110 ℃ on the supported GDC buffer layer;
and 5: by means of H2And (3) removing functional groups such as oxygen atoms, hydroxyl groups or carboxyl groups on the graphene oxide by an atmosphere thermal reduction process, so as to introduce pores into the graphene skeleton and prepare the porous graphene film.
The membrane material prepared by the process has a gas separation coefficient of 57 below that measured in a flue gas atmosphere, which is higher than a Knudsen diffusion mechanism, and CO2Has a gas passing rate of about 1.1X 10-9mol/(m2·s·Pa)。
Example 3:
a method of preparing a holey graphene membrane, comprising:
step 1: preparation of porous alpha-Al by colloid filtration method2O3Matrix: the concrete steps refer to example 1;
step 2: preparation of 8.5 wt% Gd-doped CeO by ultrasonic chemical precipitation2The specific steps of the nanoparticle sol precursor of (1) are as described in example 1;
and step 3: then depositing a layer of Ce on the alumina substrate by using a dip-coating method0.9Gd0.1O1.95(GDC) precursor film, drying and rapidly annealing to obtain a GDC buffer layer, so as to improve the bonding strength between the graphene film layer and the substrate, and the specific steps refer to example 1;
and 4, step 4: coating graphene oxide suspension with the concentration of 1.5mg/mL on alpha-Al by utilizing a spin coating process2O3Drying the graphene oxide membrane in an oven at 110 ℃ on the supported GDC buffer layer;
and 5: by means of H2And (3) removing functional groups such as oxygen atoms, hydroxyl groups or carboxyl groups on the graphene oxide by an atmosphere thermal reduction process, so as to introduce pores into the graphene skeleton and prepare the porous graphene film.
Prepared by the processThe membrane material has a gas separation coefficient of-25 measured in a flue gas atmosphere, which is slightly higher than a Knudsen diffusion mechanism, and CO2Has a gas passing rate of about 8X 10-10mol/(m2·s·Pa)。
Example 4:
a method of preparing a holey graphene membrane, comprising:
step 1: preparation of porous alpha-Al by colloid filtration method2O3Matrix: the concrete steps refer to example 1;
step 2: preparation of Gd-doped CeO by ultrasonic chemical precipitation2The nanoparticle sol precursor of (a): the concrete steps refer to example 1;
and step 3: then depositing a layer of Ce on the alumina substrate by using a dip-coating method0.9Gd0.1O1.95(GDC) precursor film, drying and rapidly annealing to obtain a GDC buffer layer, so as to improve the bonding strength between the graphene film layer and the substrate, and the specific steps refer to example 1;
and 4, step 4: coating graphene oxide suspension with concentration of 0.5mg/mL on alpha-Al by using spin coating process2O3On the supported GDC buffer layer, the graphene oxide membrane is dried in an oven at 110 DEG C
And 5: by means of H2And (3) removing functional groups such as oxygen atoms, hydroxyl groups or carboxyl groups on the graphene oxide by an atmosphere thermal reduction process, so as to introduce pores into the graphene skeleton and prepare the porous graphene film.
The membrane material prepared by the process has a gas separation coefficient of 70 measured in a flue gas atmosphere, and CO2The gas passing rate of (A) is improved by nearly one order of magnitude, about 3X 10-9mol/(m2·s·Pa)。
Example 5:
a method of preparing a holey graphene membrane, comprising:
step 1: preparation of porous alpha-Al by colloid filtration method2O3Matrix: the concrete steps refer to example 1;
step 2: preparation of 8.5 wt% Gd-doping by sonochemical precipitationCeO2The specific steps of the nanoparticle sol precursor of (1) are as described in example 1;
and step 3: then depositing a layer of Ce on the alumina substrate by using a dip-coating method0.9Gd0.1O1.95(GDC) precursor film, drying and rapidly annealing to obtain a GDC buffer layer, so as to improve the bonding strength between the graphene film layer and the substrate, and the specific steps refer to example 1;
and 4, step 4: coating graphene oxide suspension with concentration of 0.1mg/mL on alpha-Al by using spin coating process2O3Drying the graphene oxide membrane in an oven at 110 ℃ on the supported GDC buffer layer;
and 5: by means of H2And (3) removing functional groups such as oxygen atoms, hydroxyl groups or carboxyl groups on the graphene oxide by an atmosphere thermal reduction process, so as to introduce pores into the graphene skeleton and prepare the porous graphene film.
The membrane material prepared by the process has very high CO measured in the smoke atmosphere2Gas passing rate is about 1.6X 10-8mol/(m2S.pa) but the gas separation coefficient was reduced to-0.9.
The invention provides a preparation method of a porous graphene membrane and application of the porous graphene membrane in the field of carbon dioxide capture.
The experiments are only preferred examples of the present invention and are not intended to limit the scope of the present invention. It should be noted that modifications and adaptations may occur to those skilled in the art without departing from the principles of the present invention and should be considered within the scope of the present invention.
Claims (8)
1. A method of preparing a porous graphene membrane, comprising:
step 1: preparation of porous alpha-Al by colloid filtration method2O3A substrate; it is concretelyThe method comprises the following steps:
11) alpha-Al having an average particle diameter of 300nm2O3The powder was dispersed in an aqueous solution, stabilized with nitric acid pH = 2;
12) stabilizing the alpha-Al2O3Obtaining a green body by adopting a vacuum filtration technology;
13) drying the green body in air for 24 hours;
14) placing the dried green body in a muffle furnace, sintering at 950 ℃ for 10 hours in air atmosphere to obtain the disc-shaped porous alpha-Al with uniformity and no surface defect2O3A ceramic substrate;
step 2: preparation of Gd-doped CeO by ultrasonic chemical precipitation2The nanoparticle sol precursor of (a);
and step 3: in porous alpha-Al2O3Depositing a layer of Ce on the substrate0.9Gd0.1O1.95(GDC) precursor film, drying and rapid annealing process to obtain GDC buffer layer;
and 4, step 4: coating graphene oxide suspension liquid with different concentrations on alpha-Al by using spin coating process2O3Drying the supported GDC buffer layer in an oven to obtain a graphene oxide membrane;
and 5: by means of H2And (3) removing oxygen-containing functional groups on the graphene oxide by an atmosphere thermal reduction process, so as to introduce pores into the graphene skeleton, and preparing the porous graphene film.
2. The method of claim 1, wherein in step 14), the heating and cooling rates of the muffle are both 2 ℃ per minute.
3. The method for preparing the holey graphene membrane according to claim 1, wherein the step 2 comprises the following specific steps:
21) weighing ammonium ceric Nitrate (NH) according to the molar ratio of Ce to Gd of 0.9:0.14）2Ce(NO3）6And gadolinium nitrate Gd (NO)3）3·6H2O in a beaker, adding deionizationStirring the mixture to dissolve the mixture evenly;
22) putting the mixed solution into an ultrasonic degrader, carrying out 55Watts ultrasonic treatment to uniformly dissolve the solution, and dropwise adding 25wt% of TMAOH solution while carrying out ultrasonic treatment to generate GDC dispersed particles;
23) weighing a certain amount of N-diglycine, and adding the N-diglycine into the dispersion liquid to stabilize the dispersion liquid; wherein the molar ratio of the N-diglycine to the GDC is 0.05;
24) and (3) performing ultrasonic treatment on the stable dispersion liquid for 5min under the condition of 55Watts to synthesize stable GDC precursor dispersion liquid.
4. The method of claim 1, wherein in step 3, the dipping and pulling method is used to form porous α -Al2O3Deposition of Ce on the substrate0.9Gd0.1O1.95(GDC) precursor film;
drying at the drying temperature of 110 ℃ for 1 h; the rapid annealing process is to rapidly cool the temperature from 600 ℃ to room temperature within 3 min.
5. The method for preparing a porous graphene membrane according to claim 1, wherein in the step 2, Gd is doped with CeO2The doping amount of Gd in the nanoparticle sol precursor is 6-8.5 wt%.
6. The method for preparing a holey graphene membrane according to claim 1, wherein the drying temperature in step 4 is 80 to 110 ℃.
7. The method for preparing a holey graphene membrane according to claim 1, wherein, in the step 5, the H is2The temperature of the atmosphere thermal reduction process is 300 ℃, and the reaction lasts for 1 h.
8. Use of a holey graphene membrane for carbon dioxide capture, characterized in that the holey graphene membrane prepared by the method for preparing a holey graphene membrane according to any one of claims 1 to 7 is used for capturing carbon dioxide in flue gas.
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