CN112897484B - Defect-free g-C 3 N 4 Nanoplatelets, two-dimensional g-C 3 N 4 Nanosheet film and preparation method and application thereof - Google Patents
Defect-free g-C 3 N 4 Nanoplatelets, two-dimensional g-C 3 N 4 Nanosheet film and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 62
- 239000002064 nanoplatelet Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000009830 intercalation Methods 0.000 claims description 13
- 230000002687 intercalation Effects 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000007547 defect Effects 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000003828 vacuum filtration Methods 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 239000000138 intercalating agent Substances 0.000 abstract 1
- 239000002073 nanorod Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Abstract
The invention discloses a defect-free g-C 3 N 4 Nanoplatelets, two-dimensional g-C 3 N 4 A nano sheet membrane and a preparation method and application thereof. The preparation method comprises the following steps: dissolving melamine and phosphoric acid in water, performing hydrothermal treatment, filtering, and performing heating reflux treatment on the layered nanorod precursor by taking a mixture of polyalcohol and ethanol as an intercalator; cleaning, drying, heating and sintering in inert atmosphere to obtain flawless g-C 3 N 4 A nanosheet; then dispersing in solvent, depositing nano-sheet on substrate by simple vacuum filtration to obtain two-dimensional g-C for gas separation 3 N 4 A nanoplatelet film. Assembled according to the inventionThe membrane shows excellent gas separation performance, and the hydrogen permeation quantity can reach 7.23 multiplied by 10 ‑7 mol m ‑2 s ‑1 Pa ‑1 Applied to the separation of hydrogen and gas molecules with different kinetic diameters, H 2 /CO 2 The selectivity can reach 30.2, H 2 /C 3 H 6 The selectivity is over hundred, and the method has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of gas membrane separation, and in particular relates to a defect-free g-C 3 N 4 Nanoplatelets, two-dimensional g-C 3 N 4 A nano sheet membrane and a preparation method and application thereof.
Background
The gas separation is widely applied to the industrial processes of hydrogen recovery, carbon capture and storage, natural gas modification, alkane recovery, benzene derivative separation, air purification and the like. Common techniques in these processes include cryogenic distillation, and absorption and adsorption, as well as the use of membrane technology. The processes relying on heat, such as distillation and absorption, account for more than 10% of world energy consumption, increase global emissions and pollution, and membrane-based separation processes do not require heating and are therefore a competitive gas separation process. About 90% of the costs associated with heat generation will be saved by replacing the distillation process with membrane separation technology. In addition, membrane separation has other inherent advantages such as less environmental pollution (NO emissions), continuous operation, and simplicity.
Conventional polymer or zeolite membranes suffer from a tradeoff between permeability and selectivity (i.e., the upper robertson limit). Emerging two-dimensional (2D) nanoflake support membranes are expected to overcome this limitation due to their ultra-thin thickness and adjustable sieving channels. The membrane composed of these nanomaterials has much higher performance than conventional membranes and exhibits a mass transfer separation mechanism that is quite different from conventional membranes. Of these, a two-dimensional separation membrane represented by graphene (graphene) and its derivatives is most prominent. However, the gas permeation of the graphene-based membrane is still kept at 10 by low pore density and lengthy interlayer transmission channels -7 (mol m -2 s -1 Pa -1 ) In order, it is still at a low level and cannot meet the industrial needs. Two-dimensional graphite carbon nitride (g-C) 3 N 4 ) The nanoplatelets have a graphene-like layered structure, enabling their use in membrane separation processes. And intrinsic in-plane nanoporesThe nanopores are uniformly and densely distributed throughout the planar network, and can be used not only for sieving small gas molecules, but also to greatly shorten the gas transport path of the membrane. But at present g-C 3 N 4 The nano-sheets are mostly obtained by peeling from top to bottom, and in the process, the planar heptazine ring units are easily damaged, so that g-C is caused 3 N 4 Large defects (greater than +.>) Cannot be used for gas separation. For example, wang et al will find g-C from the exfoliation 3 N 4 The nano sheet has defect holes of 1-3 nm, and the obtained two-dimensional film provides more transmission channels for water molecules but cannot be used for gas separation, and has no defect of g-C 3 N 4 The nano-sheets can be used to prepare gas sieving membranes.
Disclosure of Invention
In order to solve the existing disadvantages and shortcomings, an improved bottom-up method is adopted to obtain high-quality defect-free g-C 3 N 4 A nano-sheet. In the synthesis process from bottom to top, organic solvent molecules are inserted into the assembled lamellar precursor in advance, and flawless lamellar g-C can be obtained by thermal polymerization 3 N 4 Nanosheets, g-C 3 N 4 Is layered into thin nano-sheets during thermal polycondensation. Therefore, no further exfoliation is required, and thus non-selective defects due to structural failure can be largely avoided. Based on defect-free g-C 3 N 4 The nano-sheet is assembled with g-C used for gas separation by adopting a vacuum suction filtration mode 3 N 4 A nanoplatelet film. The primary purpose of the invention is to producePreparing defect-free g-C 3 N 4 The nano-sheet can be used for assembling films in the field of gas separation. The present invention provides a defect-free g-C 3 N 4 Nanoplatelets, two-dimensional g-C 3 N 4 A nano sheet membrane and a preparation method and application thereof.
The aim of the invention is achieved by the following technical scheme.
Defect-free g-C 3 N 4 The preparation method of the nano-sheet comprises the following steps:
(1) Adding melamine and phosphoric acid into deionized water, and performing constant-temperature water bath until the solid is completely dissolved;
(2) Carrying out hydrothermal treatment on the solution obtained in the step (1), and filtering to obtain a layered micro-rod precursor;
(3) Washing the layered micro-rod precursor in the step (2) with deionized water for 2-3 times, and then drying at 60-80 ℃ to obtain white powder;
(4) Heating and refluxing the white powder obtained in the step (3) by taking a mixture of polyalcohol and ethanol as an intercalation agent to obtain layered precursor powder after organic solvent molecule intercalation; washing the layered precursor powder with ethanol, and then drying at 60-80 ℃;
(5) Sintering (stripping and planar polymerization) the dried layered precursor powder in the step (4) under inert gas atmosphere to obtain flawless g-C 3 N 4 A nano-sheet.
Preferably, in the step (1), the mole ratio of the melamine to the phosphoric acid is 1:1-2:1, the temperature of the constant-temperature water bath is 70-90 ℃, and the time of the constant-temperature water bath is 0.5-1 h; in the step (2), the time of the hydrothermal treatment is 10-12 h, and the temperature of the hydrothermal treatment is 160-180 ℃.
Preferably, in the step (4), the polyol is glycerol, the volume ratio of the polyol to the ethanol in the mixed solution is 2:1-3:1, and the temperature of the reflux treatment is 80-90 ℃; the time of the reflux treatment is 2-4 hours; further preferably, the volume ratio of the polyol to the ethanol in the mixed solution is 2:1.
Preferably, in step (5), theThe inert gas is nitrogen, and the flow rate of the inert gas is 100-200mL/min; the sintering temperature is 520-550 ℃, the sintering time is 2-4 h, and the sintering temperature rising rate is 2-5 ℃/min; further preferably, the temperature rise rate of sintering is 2 ℃/min. g-C is caused by ammonia gas obtained in the melamine decomposition process 3 N 4 Defects are generated, and the generated ammonia gas is driven off in an inert atmosphere to obtain more complete g-C 3 N 4 A nanopore structure. Thus, we selected inert nitrogen operating conditions.
The preparation method can prepare flawless g-C 3 N 4 A nano-sheet.
Two-dimensional g-C 3 N 4 The preparation method of the nano sheet film comprises the following steps:
(a) The above-mentioned defect-free g-C 3 N 4 Dispersing the nano-sheets in a mixed solution of deionized water and isopropanol to obtain g-C 3 N 4 A nanosheet suspension;
(b) g-C as described in step (a) 3 N 4 Nanosheet suspension is filtered under vacuum using porous support on which g-C is prepared 3 N 4 A membrane;
(c) g-C as described in step (b) 3 N 4 Vacuum drying the membrane to obtain two-dimensional g-C supported on porous carrier 3 N 4 A nanoplatelet film.
Preferably, in the step (a), the volume ratio of deionized water to isopropanol in the mixed solution is 1:1-3:1, and the g-C is as follows 3 N 4 g-C in nanosheet suspension 3 N 4 The concentration of the nano-sheet is 0.005-0.02 mg/mL; further preferably, the volume ratio of deionized water and isopropyl alcohol in the mixed solution is 1:1 (v: v).
Preferably, in the step (b), the porous carrier is an anodic aluminum oxide film AAO, and the pore diameter of the porous carrier is 160-200 nm; in the step (c), the time of vacuum drying is more than 24 hours, and the temperature of vacuum drying is room temperature.
The two-dimensional g-C prepared by the preparation method 3 N 4 Nanosheet filmThe two-dimensional g-C 3 N 4 The thickness of the nano sheet film is 0.15-1 mu m.
The two-dimensional g-C 3 N 4 The application of the nano sheet membrane in the field of gas separation.
Preferably, the specific application process is as follows: the g-C obtained was then subjected to 3 N 4 The films were packaged using a domestic wicker-kalenbach apparatus for gas testing. Gas molecules (H) having different kinetic diameters 2 ,CO 2 ,N 2 ,CH 4 ,C 3 H 6 ,C 3 H 8 ) By said g-C 3 N 4 Nanosheet film, film pair H 2 /CO 2 The selectivity can reach 30.2, H 2 /C 3 H 6 Selectivity is over hundred.
Compared with the prior art, the invention has the following advantages:
(1) The g-C obtained 3 N 4 The nano-sheets are defect-free, and the assembled membrane can be used for separating gas molecules with smaller size
(2) The g-C obtained 3 N 4 The nano sheet membrane has ultrahigh hydrogen flux and excellent stability, and the hydrogen permeation capacity can reach 7.23 multiplied by 10 -7 mol m -2 s -1 Pa -1 Meets the requirements in the industrial production process and has wide application prospect.
(3) The g-C obtained 3 N 4 The nano sheet membrane shows excellent gas separation performance, and is applied to separation of hydrogen and gas molecules with different kinetic diameters, H 2 /CO 2 The selectivity can reach 30.2, H 2 /C 3 H 6 Selectivity is over hundred.
Drawings
FIG. 1 shows defect-free g-C obtained in example 1 3 N 4 (a) SEM and (b) AFM images of the nanoplatelets.
FIG. 2 is a two-dimensional g-C obtained in example 1 3 N 4 SEM images of (a) surface and (b) cross-section of nanoplatelets film.
FIG. 3 is a two-dimensional g-C obtained in example 1 3 N 4 The nano sheet film is used for single gas performance diagram in various gas molecular tests.
FIG. 4 is a two-dimensional g-C obtained in example 1 3 N 4 Stability profile of nanoplatelet films for continuous operation for up to 300 days.
Detailed Description
The following describes the technical scheme of the present invention in further detail by referring to examples, but the embodiments and the protection scope of the present invention are not limited thereto.
Example 1
Defect-free g-C 3 N 4 Nanoplatelets, two-dimensional g-C 3 N 4 The preparation method of the nano sheet film specifically comprises the following steps:
(1) Synthesizing a layered precursor: firstly, 1.0g of melamine and 1.2g of phosphoric acid are weighed, mixed with 100ml of deionized water, and heated in a constant temperature water bath at 80 ℃ for 1 hour until the melamine and the phosphoric acid are completely dissolved. And transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene substrate while the solution is hot, and reacting for 12 hours at 180 ℃ to obtain the layered micro-rod precursor. The mixture obtained after filtering and washing with deionized water is dried in an oven at 60 ℃ for 10 hours, and the obtained white powder is a layered precursor;
(2) Synthesizing a layered precursor after organic solvent molecule intercalation: the layered precursor obtained previously was heated to reflux with 20ml of a mixed solution of ethanol and glycerol (2:1, v:v) at 90℃for 3 hours. Washing the powder obtained after reflux with ethanol for multiple times, and drying in an oven at 60 ℃ for 10 hours to obtain a layered precursor after intercalation of organic solvent molecules;
(3) Preparation of defect-free g-C 3 N 4 Nanosheets: at N 2 Under the condition (100 mL/min), heating the layered precursor after intercalation of organic solvent molecules to 550 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2h to obtain flawless g-C 3 N 4 A nanosheet;
for g-C obtained in step (3) 3 N 4 g-C in two-dimensional nanoplatelet solution 3 N 4 Two-dimensional nanoplatelet SEM andthe results of the AFM test are shown in fig. 1, and can be seen from fig. 1: g-C 3 N 4 No defects exist on the two-dimensional nanoplatelets, and the thickness of the nanoplatelets is about 3nm.
(4) Preparation of g-C 3 N 4 Nanosheet film: taking 1mg of the obtained g-C 3 N 4 The nanoplatelets are dispersed in 50ml of a mixed solution of deionized water and isopropyl alcohol in a ratio of 1:1 (v: v). Obtaining g-C with the concentration of 0.02mg/mL 3 N 4 Nanosheet suspensions. A vacuum filtration system is adopted to filter a certain amount of g-C respectively 3 N 4 The nano-sheet suspension is prepared into g-C with different thickness on anodic alumina carrier with aperture of 160-200 nm 3 N 4 And (3) a film. Vacuum drying the membrane obtained by suction filtration at room temperature for more than 24 hours to remove residual solvent in the membrane, thereby obtaining two-dimensional g-C supported on a porous carrier 3 N 4 A nanoplatelet film.
For g-C with different thickness obtained in the step (4) 3 N 4 The two-dimensional nanoplatelet films were subjected to SEM testing, the results are shown in fig. 2, and can be seen from fig. 2: the film surface is intact with no detectable pinholes or cracks.
For g-C obtained in step (4) 3 N 4 The two-dimensional nanoplatelet films were subjected to gas separation tests, the results of which are shown in fig. 3, and can be seen from fig. 3: g-C 3 N 4 The single gas permeation quantity of hydrogen, carbon dioxide, nitrogen, methane, propylene and propane of the two-dimensional nano sheet film is 7.24 multiplied by 10 -7 mol m -2 s -1 Pa -1 、2.93×10 -8 mol m -2 s -1 Pa -1 、6.09×10 -8 mol m -2 s -1 Pa -1 、5.93×10 - 8 mol m -2 s -1 Pa -1 、8.59×10 -9 mol m -2 s -1 Pa -1 6.59X10 -9 mol m -2 s -1 Pa -1 。H 2 For CO 2 、CH 4 、N 2 、C 3 H 6 And C 3 H 8 The selectivities of (2) are 30.2, 14, 15, 103.6 and 135, respectively, far exceeding the corresponding knoop diffusion.
Step by step(4) The g-C obtained 3 N 4 H two-dimensional nanosheet film 2 /CO 2 The stability test, the results of which are shown in fig. 4, can be seen from fig. 4: the membranes were stable in separation performance over a three hundred day long term test even when stored in the environment for 200 days without any introduction of protective gas.
Example 2
Defect-free g-C 3 N 4 Nanoplatelets, two-dimensional g-C 3 N 4 The preparation method of the nano sheet film specifically comprises the following steps:
(1) Synthesizing a layered precursor: first, 1.12g of melamine and 1.23g of phosphoric acid were weighed, mixed with 50ml of deionized water and heated in a thermostatic water bath at 80℃for 0.5h. And transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene substrate while the solution is hot, and reacting for 10 hours at 180 ℃ to obtain the layered micro-rod precursor. Washing the mixture obtained after water heating with deionized water for several times, and drying in an oven at 60 ℃ for 10 hours to obtain white powder which is a layered precursor;
(2) Synthesizing a layered precursor after organic solvent molecule intercalation: the layered precursor obtained previously was heated to reflux with 20ml of a mixed solution of ethanol and glycerol (2:1, v:v) at 90℃for 2 hours. Washing the powder obtained after reflux with ethanol for multiple times, and drying in an oven at 60 ℃ for 12 hours to obtain a layered precursor after intercalation of organic solvent molecules;
(3) Preparation of defect-free g-C 3 N 4 Nanosheets: at N 2 Under the condition (200 mL/min), heating the layered precursor after intercalation of organic solvent molecules to 520 ℃ at a heating rate of 2 ℃/min, and preserving heat for 4 hours to obtain flawless g-C 3 N 4 A nanosheet;
(4) Preparation of g-C 3 N 4 Nanosheet film: taking 1mg of the obtained g-C 3 N 4 The nanoplatelets are dispersed in 50ml of a mixed solution of deionized water and isopropyl alcohol in a ratio of 2:1 (v: v). Obtaining g-C with the concentration of 0.02mg/mL 3 N 4 Nanosheet suspensions. A vacuum filtration system is adopted to filter a certain amount of g-C respectively 3 N 4 The nanosheet suspension is prepared on an anodic aluminum oxide carrier with the aperture of 160-200 nmg-C of the same thickness 3 N 4 And (3) a film. Vacuum drying the membrane obtained by suction filtration at room temperature for more than 24 hours to remove residual solvent in the membrane, thereby obtaining two-dimensional g-C supported on a porous carrier 3 N 4 A nanoplatelet film.
Example 3
Defect-free g-C 3 N 4 Nanoplatelets, two-dimensional g-C 3 N 4 The preparation method of the nano sheet film specifically comprises the following steps:
(1) Synthesizing a layered precursor: firstly, 1.05g of melamine and 1.27g of phosphoric acid are weighed, mixed with 100ml of deionized water and heated in a constant temperature water bath at 80 ℃ for 1 hour until the melamine is completely dissolved. And transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene substrate while the solution is hot, and reacting for 10 hours at 180 ℃ to obtain the layered micro-rod precursor. Washing the mixture obtained after water heating with deionized water for several times, and drying in an oven at 60 ℃ for 10 hours to obtain white powder which is a layered precursor;
(2) Synthesizing a layered precursor after organic solvent molecule intercalation: the layered precursor obtained previously was heated to reflux with 20ml of a mixed solution of ethanol and glycerol (2:1, v:v) at 90℃for 4 hours. Washing the powder obtained after reflux with ethanol for multiple times, and drying in an oven at 60 ℃ for 13 hours to obtain a layered precursor after intercalation of organic solvent molecules;
(3) Preparation of defect-free g-C 3 N 4 Nanosheets: at N 2 Under the condition (150 mL/min), heating the layered precursor after intercalation of organic solvent molecules to 520 ℃ at a heating rate of 2 ℃/min, and preserving heat for 2h to obtain flawless g-C 3 N 4 A nanosheet;
(4) Preparation of g-C 3 N 4 Nanosheet film: taking 0.5mg of the obtained g-C 3 N 4 The nanoplatelets are dispersed in 50ml of a mixed solution of deionized water and isopropyl alcohol in a ratio of 3:1 (v: v). Obtaining g-C with the concentration of 0.01mg/mL 3 N 4 Nanosheet suspensions. A vacuum filtration system is adopted to filter a certain amount of g-C respectively 3 N 4 The nano-sheet suspension is prepared into g-C with different thickness on anodic alumina carrier with aperture of 160-200 nm 3 N 4 And (3) a film. Vacuum drying the membrane obtained by suction filtration at room temperature for more than 24 hours to remove residual solvent in the membrane, thereby obtaining two-dimensional g-C supported on a porous carrier 3 N 4 A nanoplatelet film.
The foregoing examples are illustrative of the present invention and are not intended to be limiting, and other changes, combinations, modifications, and simplifications that do not depart from the spirit and principles of the invention are intended to be within the scope of the invention.
Claims (5)
1. Two-dimensional g-C 3 N 4 The application of the nano sheet membrane in the field of gas separation is characterized in that the two-dimensional g-C 3 N 4 The thickness of the nano sheet film is 0.15-1 mu m;
the two-dimensional g-C 3 N 4 The preparation method of the nano sheet film comprises the following steps:
(a) Will be defect free g-C 3 N 4 Dispersing the nano-sheets in a mixed solution of deionized water and isopropanol to obtain g-C 3 N 4 A nanosheet suspension;
(b) g-C as described in step (a) 3 N 4 Nanosheet suspension is filtered under vacuum using porous support on which g-C is prepared 3 N 4 A membrane; the aperture of the porous carrier is 160-200 nm;
(c) g-C as described in step (b) 3 N 4 Vacuum drying the membrane to obtain two-dimensional g-C supported on porous carrier 3 N 4 A nanoplatelet film;
said defect-free g-C 3 N 4 The preparation method of the nano-sheet comprises the following steps:
(1) Adding melamine and phosphoric acid into deionized water, and performing constant-temperature water bath until the solid is completely dissolved; the mole ratio of the melamine to the phosphoric acid is 1:1-2:1;
(2) Carrying out hydrothermal treatment on the solution obtained in the step (1), and filtering to obtain a layered micro-rod precursor; the time of the hydrothermal treatment is 10-12 h, and the temperature of the hydrothermal treatment is 160-180 ℃;
(3) Washing the layered micro-rod precursor in the step (2) with deionized water for 2-3 times, and then drying at 60-80 ℃ to obtain white powder;
(4) Heating and refluxing the white powder obtained in the step (3) by taking a mixture of polyalcohol and ethanol as an intercalation agent to obtain layered precursor powder after organic solvent molecule intercalation; washing the layered precursor powder with ethanol, and then drying at 60-80 ℃; the polyol is glycerol, the volume ratio of the polyol to the ethanol in the mixed solution is 2:1-3:1, and the temperature of the reflux treatment is 80-90 ℃; the time of the reflux treatment is 2-4 hours;
(5) Sintering the dried layered precursor powder in the step (4) under the inert gas atmosphere condition to obtain flawless g-C 3 N 4 A nanosheet; the sintering temperature is 520-550 ℃, and the sintering time is 2-4 h.
2. The use according to claim 1, wherein in step (1), the temperature of the thermostatic water bath is 70-90 ℃ and the time of the thermostatic water bath is 0.5-1 h.
3. The use according to claim 1, wherein in step (5), the inert gas is nitrogen and the flow rate of the inert gas is 100-200mL/min; the temperature rising rate of the sintering is 2-5 ℃/min.
4. The use according to claim 1, wherein in step (a), the volume ratio of deionized water and isopropyl alcohol in the mixed solution is 1:1-3:1, and the g-C is as follows 3 N 4 g-C in nanosheet suspension 3 N 4 The concentration of the nano-sheet is 0.005-0.02 mg/mL.
5. The use according to claim 1, wherein in step (b) the porous support is an anodic aluminium oxide film AAO; in the step (c), the time of vacuum drying is more than 24 hours, and the temperature of vacuum drying is room temperature.
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