CN114733372A - Preparation method and application of black phosphorus alkene-MXene composite membrane - Google Patents
Preparation method and application of black phosphorus alkene-MXene composite membrane Download PDFInfo
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- CN114733372A CN114733372A CN202210377184.8A CN202210377184A CN114733372A CN 114733372 A CN114733372 A CN 114733372A CN 202210377184 A CN202210377184 A CN 202210377184A CN 114733372 A CN114733372 A CN 114733372A
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- black phosphorus
- phosphorus alkene
- mxene
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- 239000012528 membrane Substances 0.000 title claims abstract description 76
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 black phosphorus alkene Chemical class 0.000 claims abstract description 58
- 239000007789 gas Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 206010034962 Photopsia Diseases 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 238000010926 purge Methods 0.000 claims abstract description 11
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 238000001514 detection method Methods 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 238000001338 self-assembly Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000002135 nanosheet Substances 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000004817 gas chromatography Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000005457 ice water Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000065 phosphene Inorganic materials 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- AMCYFOSVYJWEBU-UHFFFAOYSA-N tetrabutylazanium borate Chemical compound [O-]B([O-])[O-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC AMCYFOSVYJWEBU-UHFFFAOYSA-N 0.000 description 3
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical compound C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 description 2
- YYAVXASAKUOZJJ-UHFFFAOYSA-N 4-(4-butylcyclohexyl)benzonitrile Chemical compound C1CC(CCCC)CCC1C1=CC=C(C#N)C=C1 YYAVXASAKUOZJJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Images
Classifications
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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
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method and application of a black phosphorus alkene-MXene composite membrane, which comprises the following steps: electrochemically stripping to obtain black phosphorus, mixing the black phosphorus with the solution, performing ultrasonic treatment, centrifugal washing, and freeze drying to obtain black phosphorus alkene powder; three-dimensionally layered Ti3AlC2Adding the powder into a mixed solution of lithium salt and an acid solution, uniformly stirring, centrifugally washing, and freeze-drying to obtain MXene powder; adding the black phosphorus alkene powder and MXene powder into a brown reagent bottle, ultrasonically mixing, stacking on a substrate by a nano self-assembly technology, and drying to obtain a black phosphorus alkene-MXene composite film; compounding black phosphene-MXeneAnd putting the combined membrane into a gas separation device, introducing mixed gas to be separated at a feed side, and introducing a purge gas at a permeation side for detection. The black phosphorus alkene-MXene composite membrane has good stability and higher H2The permeation quantity and the gas selectivity are high, and the purity of the separated hydrogen is higher; no substrate is needed, the preparation process is simple, the energy consumption is low, and the cost can be greatly saved in practical application.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a preparation method and application of a black phosphorus alkene-MXene composite membrane.
Background
Hydrogen, as a clean energy source, is present in increasing proportions in energy structures at the present stage. The utilization of hydrogen often faces the separation and purification of hydrogen, the traditional cryogenic rectification and pressure swing adsorption separation of hydrogen has more limitations on application occasions and high energy consumption, and the membrane method for separating hydrogen has low energy consumption, wide application occasions and high purity of separated hydrogen, so that the membrane method for separating and purifying hydrogen has very important significance for the large-scale application of hydrogen energy.
The existing hydrogen separation membrane material mainly comprises a metal and metal alloy membrane, a polymer membrane, an inorganic ceramic membrane, a two-dimensional ceramic membrane and the like. The metal and metal alloy membranes are mainly noble metals, such as metal palladium membranes and palladium-silver alloy membranes, and the hydrogen permeable membranes of the materials generally have good selectivity and permeation flux, but have the problems of high cost, hydrogen brittleness and the like. The polymer membrane generally has poor chemical stability and is easily corroded by an acid atmosphere, and a Robertson upper limit of the trade-off exists between the selectivity and the permeation flux of the polymer membrane. The inorganic ceramic membrane has good stability and selectivity, but has the problems of low hydrogen permeation amount, difficult high-temperature sealing and the like.
At present, there are many two-dimensional materials applied to hydrogen membrane separation, such as: graphene, graphene oxide, black phosphorus, molybdenum disulfide, metal organic framework Materials (MOF), MXene, and the like. The black phosphorus alkene membrane has been verified to have good hydrogen separation performance, and has high-level selectivity and high-level hydrogen permeation flux, but the black phosphorus alkene membrane is easy to oxidize in the application process, namely when the black phosphorus alkene membrane is placed in an air environment, the black phosphorus alkene membrane can quickly react with water and oxygen in the air to generate phosphoric acid to degrade, so that the stability of the black phosphorus alkene membrane must be improved in order to improve the practical application value of the black phosphorus alkene membrane.
Because P on the surface of the black phosphorus has a pair of lone-pair electrons, and Ti on the surface of MXene has an empty orbit, a P-O-Ti bond can be formed between the two after the two are compounded, and the oxidative degradation of the black phosphorus alkene can be reduced. Therefore, the preparation method and the application of the black phosphene-MXene composite membrane are provided for improving the stability of the black phosphene.
Disclosure of Invention
In order to solve the technical problems, the invention designs a preparation method and application of a black phosphorus alkene-MXene composite membrane, which comprises the steps of preparing black phosphorus alkene dispersion liquid by using massive black phosphorus and preparing Ti by using Ti3AlC2The invention discloses a method for preparing a multilayer Mxene dispersion liquid, a method for preparing a black phosphene-MXene composite membrane and application of the black phosphene membrane to the field of gas separation, and the black phosphene-MXene composite membrane prepared by the method disclosed by the invention has ultrahigh H2The penetration amount,Ultra-high H2/CO2,H2/N2And H2/CH4Separation selectivity and excellent mechanical properties.
In order to achieve the technical effects, the invention is realized by the following technical scheme: a preparation method of a black phosphorus alkene-MXene composite membrane is characterized by comprising the following steps:
step 1: electrochemically stripping the blocky black phosphorus in an organic solvent of organic salt to obtain fluffy black phosphorus;
step 2: mixing fluffy black phosphorus with the solution, performing ultrasonic treatment and centrifugal washing to obtain supernatant, namely the solution containing the black phosphorus alkene nanosheets, and performing freeze drying to obtain black phosphorus alkene powder;
step 3: mixing lithium salt with acid solution to obtain mixed solution; then three-dimensionally layered Ti3AlC2Adding the powder into the mixed solution, uniformly stirring, centrifugally washing, and freeze-drying to obtain MXene powder;
step 4: adding the black phosphorus alkene powder obtained in Step2 and MXene powder obtained in Step3 into a brown reagent bottle according to the mass percentage of 1:1, ultrasonically mixing, stacking the compounded dispersion liquid on a substrate through a nano sheet self-assembly technology, and drying to obtain the black phosphorus alkene-MXene composite membrane.
Further, the organic salt in Step1 is one of tetrabutylammonium bromide and tetrabutylammonium tetrafluoroborate; the organic solvent is one of acetonitrile, N-Dimethylformamide (DMF) and N-methylpyrrolidone (NMP); the mass ratio of the black phosphorus to the organic salt is 1: 12; the mass volume ratio of the organic salt to the organic solvent is 1.2g to 20 ml; the electrochemical stripping adopts a direct-current stabilized power supply as a power supply; the voltage is 3-10V; the current is 1-15 mA.
Further, the organic solvent in Step2 is one of N, N-Dimethylformamide (DMF) and N-methylpyrrolidone (NMP); the mass volume ratio of the black phosphorus to the organic solvent is 0.1g to 80 ml; the ultrasonic power is 300-500W; the ultrasonic time is 1-3 hours, and the ultrasonic temperature is 0-10 ℃; the rotating speed of the centrifugation is 3000-13000 rpm; centrifuging for 5-60 min; the washing is carried out for 3-10 times by using deionized water.
Further, the lithium salt in Step3 is one of lithium chloride and lithium fluoride; the acid solution is one of hydrofluoric acid and hydrochloric acid; the mass volume ratio of the lithium salt to the acid solution is 1g (30-80) mL; the centrifugation rate was 3000-8000 rap/min.
Further, the ultrasonic condition in Step4 is 120-300W, and the temperature is 10-20 ℃; the nano assembly technology is one of a spin coating method, a spraying method, a natural drying method and a vacuum filtration method; the substrate is an Anodic Aluminum Oxide (AAO) film substrate, the aperture is 200nm, and the diameter is 10-200 mm; the drying condition is one or more of drying in an air drying oven and vacuum drying; the drying temperature is 10-80 ℃: the drying time is 10-72 hours.
Another object of the present invention is to provide an application of a black phosphorus alkene-MXene composite film, which comprises the following steps:
(1) putting the black phosphorus alkene-MXene composite membrane into a gas separation device, and then introducing mixed gas to be separated with different kinetic diameters into a feeding side;
(2) introducing a purge gas at the purge side;
(3) and (3) introducing the purge gas in the step (2) into a gas chromatograph for detection, so as to obtain the permeation amount and selectivity of different gases.
Further, the thickness of the black phosphorus alkene-MXene composite membrane is 1-3 μm; the mixed gas is hydrogen (H)20.29nm), carbon dioxide (CO)20.33nm), nitrogen (N)20.364nm), methane (CH)40.4nm), e.g. H2/CO2,H2/N2And H2/CH4One or more combinations thereof.
Further, the purge gas is argon; the flow of the purging gas is 10-1000 ml/min; the gas chromatography is Fuli GC970 II gas chromatography.
The invention has the beneficial effects that:
(1) the black phosphorus alkene-MXene composite membrane is used for separating the componentsHas H2The mixed gas has good stability, avoids the possible degradation of pure black phosphorus alkene, and has higher H2The permeation amount and the high gas selectivity can inhibit the permeation amount of some gas molecules with larger kinetic diameters to be extremely low, and the purity of the separated hydrogen is higher.
(2) The black phosphorus alkene-MXene composite membrane is a self-supporting membrane, does not need any substrate, is simple in preparation process and low in energy consumption, and can greatly save cost in practical application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a composite black phospholene-MXene film prepared in example 1;
FIG. 2 is a cross-sectional scanning electron microscope image of the black phosphene-MXene composite film prepared in example 1;
FIG. 3 is a comparative XRD analysis diagram of a black phosphene-MXene composite membrane prepared in example 1;
FIG. 4 is a graph showing the selective analysis of the black phosphene-MXene composite membrane prepared in example 1 applied to gas separation;
FIG. 5 is a graph comparing degradation of a black phospholene-MXene composite membrane and a pure black phospholene membrane.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1 to 5, a method for preparing a black phosphorus alkene-MXene composite film includes the following steps:
(1) 1.0g of Ti3AlC2The powder and 1.0g LiF powder were placed in a Teflon beaker; adding 30ml of 8mol/L hydrochloric acid solution, stirring uniformly, then placing the beaker in a water bath, magnetically stirring for 48 hours at 60 ℃, and introducing argon for protection during stirring; and after stirring, centrifugally washing the materials by using deionized water, washing at 4000r/min for 10min until the pH value is about 6, finishing washing, and freeze-drying to obtain the multi-layer MXene powder.
(2) Preparing 1.2g of tetrabutylammonium bromide and 20ml of acetonitrile into electrolyte; cutting 0.1g of block black phosphorus into a plurality of small blocks, and then electrochemically stripping the small blocks of black phosphorus in electrolyte by adopting a direct-current voltage-stabilizing power supply to obtain fluffy black phosphorus; and (3) ultrasonically treating the obtained fluffy black phosphorus in 80ml of N, N-Dimethylformamide (DMF) for 90 minutes, then centrifuging at the rotating speed of 3000rpm for 10 minutes, taking supernatant, centrifuging and washing at the rotating speed of 8000rpm, finishing washing, and freeze-drying to obtain the multi-layer black phosphorus alkene powder.
(3) Respectively preparing the obtained black phosphorus alkene powder and MXene powder into 0.15mg/mL dispersion liquid, placing 30mL of black phosphorus alkene dispersion liquid and 30mL of MXene dispersion liquid into a brown reagent bottle, introducing argon, sealing by using a sealing film, carrying out ultrasonic treatment on the mixed solution in the reagent bottle for 90min in an ice water bath at 150W, carrying out vacuum filtration on the solution containing the black phosphorus alkene and MXene nanosheets, accumulating the solution on an alumina substrate with the aperture of 200nm and the diameter of 15mm, and drying for 24 hours at 35 ℃ in a vacuum drying oven to obtain the black phosphorus alkene-MXene composite film.
The application of the black phosphorus alkene-MXene composite membrane in gas membrane separation comprises the following steps:
putting the black phosphorus alkene-MXene composite membrane into a gas separation device, and respectively introducing 100mL/min H at the feed side2/CO2,H2/N2And H2/CH4In which H is2The partial pressure is 0.5atm, Ar of 200mL/min is used for blowing and then the gas chromatography is used for detection. The permeation amount of various gases is measured through experiments as follows: pH2＝380GPU，PN2＝6.78GPU，PCO25.78GPU and PCH4＝9.43GPU(1GPU＝1×10-6cm3/cm2Sec cmHgatSTP). The results are shown in FIG. 3. Separation selectivity is respectively H2/N2＝56.44，H2/CO263.44 and H2/CH4The results are shown in fig. 4, 39.74.
Example 2
A preparation method of a black phosphorus alkene-MXene composite film comprises the following steps:
(1) 1.0g of Ti3AlC2Placing the powder and 5 wt% of hydrofluoric acid powder in a polytetrafluoroethylene beaker, then placing the beaker in a water bath kettle, magnetically stirring for 36 hours at 60 ℃, and introducing argon gas for protection during stirring; and after stirring is finished, repeatedly centrifuging and washing the materials by using deionized water, wherein the centrifugal speed is 3500r/min, the washing time is 10min each time, the washing is carried out until the pH value of the solution is about 6, and the supernatant is the solution containing MXene nanosheets, and the concentration of the supernatant is 0.18 mg/mL.
(2) Preparing electrolyte from 1.5g of tetrabutylammonium borate and 20ml of acetonitrile; cutting 0.15g of block black phosphorus into a plurality of small blocks, and then electrochemically stripping the small blocks of black phosphorus in electrolyte by adopting a direct-current voltage-stabilizing power supply to obtain fluffy black phosphorus; and (3) ultrasonically treating the obtained fluffy black phosphorus in 80mL of N-methylpyrrolidone (NMP) for 90 minutes, then centrifuging at the rotating speed of 3000rpm for 10 minutes, taking supernatant, centrifuging and washing at the rotating speed of 8000rpm, and preparing a dispersion liquid after washing is finished, wherein the dispersion liquid is a solution containing black phosphorus alkene nanosheets, and the concentration of the dispersion liquid is 0.25 mg/mL.
(3) And (3) placing 20mL and 30mL of MXene dispersion liquid of the obtained black phosphorus alkene dispersion liquid into a brown reagent bottle, introducing argon, sealing by using a sealing film, carrying out ultrasonic treatment on the mixed solution in the reagent bottle for 60min under 270W in an ice-water bath, carrying out vacuum suction filtration on the solution containing the black phosphorus alkene and MXene nanosheets, stacking the solution on a polyether sulfone (PES) filter membrane substrate with the aperture of 500nm and the diameter of 15mm, and drying for 12 hours in a vacuum drying oven at 50 ℃ to obtain the black phosphorus alkene-MXene composite membrane.
The application of the black phosphorus alkene-MXene composite membrane in gas membrane separation comprises the following steps:
respectively introducing 100mL/min of H at the feed side2/N2In which H is2The partial pressure is 0.5atm, Ar of 100mL/min is used for blowing and then the gas chromatography is used for detection. The permeation amount of various gases is measured through experiments as follows: pH2＝361GPU，PN2＝6.54GPU。H2/N2The separation selectivity was 55.19.
Example 3
A preparation method of a black phosphorus alkene film comprises the following steps:
(1) 2.0g of Ti3AlC2Placing the powder and 10 wt% of hydrofluoric acid powder in a polytetrafluoroethylene beaker, then placing the beaker in a water bath kettle, magnetically stirring for 48 hours at 60 ℃, and introducing argon gas for protection during stirring; and after stirring is finished, repeatedly centrifuging and washing the materials by using deionized water, wherein the centrifugation speed is 4000r/min, the washing time is 15min each time, the washing is carried out until the pH value of the solution is about 6, and the supernatant is the solution containing MXene nanosheets, and the concentration of the supernatant is 0.24 mg/mL.
(2) 1g of tetrabutylammonium borate is dissolved in 20mL of N, N-Dimethylformamide (DMF) to be used as electrolyte; taking 0.2g of blocky black phosphorus, cutting the blocky black phosphorus into a plurality of small blocks, and electrochemically stripping the blocky black phosphorus by adopting a direct-current stabilized voltage power supply and prepared electrolyte in multiple times to obtain fluffy black phosphorus; and (3) ultrasonically treating the fluffy black phosphorus in 80ml N-methyl pyrrolidone (NMP) for 90 minutes, then centrifuging at the rotating speed of 3000rpm for 10 minutes, taking supernatant, centrifugally washing at the rotating speed of 12000rpm, finishing washing, and freeze-drying to obtain the multilayer black phosphorus alkene powder.
(3) Preparing the obtained black phosphorus alkene powder into 0.15mg/mL dispersion liquid, mixing 25mL of black phosphorus alkene dispersion liquid with 15mL of MXene-containing nanosheet dispersion liquid, placing the mixture into a brown reagent bottle, introducing argon, sealing with a sealing film, carrying out ultrasonic treatment on the mixed solution in the reagent bottle for 45min in an ice-water bath under 300W, carrying out vacuum filtration on the solution containing the black phosphorus alkene and the MXene nanosheet, accumulating the solution on an aluminum oxide substrate with the aperture of 200nm and the diameter of 15mm, and drying for 18 hours at the temperature of 60 ℃ in a vacuum drying oven to obtain the black phosphorus alkene-MXene composite film.
The application of the black phosphorus alkene-MXene composite membrane in gas membrane separation comprises the following steps:
100mL/min of H is respectively introduced into the feed side2/CH4In which H is2The partial pressure is 0.5atm, Ar of 100mL/min is used for blowing and then the gas chromatography is used for detection. The permeation amount of various gases is measured by experiments as follows: pH2＝376GPU，PCH4＝8.93GPU。H2/CH4The separation selectivity was 42.1.
Example 4
The stability of the black phosphene-MXene composite membrane is compared with that of the black phosphene membrane
(1) Preparing electrolyte from 1.5g of tetrabutylammonium borate and 20ml of acetonitrile; cutting 0.15g of block black phosphorus into a plurality of small blocks, and then electrochemically stripping the small blocks of black phosphorus in electrolyte by adopting a direct-current voltage-stabilizing power supply to obtain fluffy black phosphorus; and (3) ultrasonically treating the obtained fluffy black phosphorus in 80mL of N-methylpyrrolidone (NMP) for 90 minutes, then centrifuging at the rotating speed of 3000rpm for 10 minutes, taking supernatant, centrifuging and washing at the rotating speed of 8000rpm, and preparing a dispersion liquid after washing is finished, wherein the dispersion liquid is a solution containing the black phosphorus alkene nano-sheets, and the concentration is 0.25 mg/mL. And (3) vacuum filtering the solution containing the black phosphorus alkene nanosheets, accumulating the solution on an alumina substrate with the aperture of 200nm and the diameter of 15mm, and drying the solution in a vacuum drying oven at the temperature of 35 ℃ for 12 hours to obtain the black phosphorus alkene membrane.
(2) 1.0g of Ti3AlC2Placing the powder and 5 wt% of hydrofluoric acid powder in a polytetrafluoroethylene beaker, then placing the beaker in a water bath kettle, magnetically stirring for 36 hours at 60 ℃, and introducing argon gas for protection during stirring; after stirring, repeatedly centrifuging and washing the material by using deionized water at 3500r/min for 10min each time until the pH value of the solution is about 6, wherein the supernatant is a solution containing MXene nanosheets and has the concentration of 0.18 mg/mL; placing 30mL and 20mL of MXene dispersion liquid of the obtained black phosphorus alkene dispersion liquid into a brown reagent bottle, introducing argon gas, sealing by using a sealing film, carrying out ultrasonic treatment on the mixed solution in the reagent bottle for 60min under 270W in an ice water bath, carrying out vacuum suction filtration on the solution containing the black phosphorus alkene and MXene nanosheets, stacking the solution on a polyether sulfone (PES) filter membrane substrate with the aperture of 500nm and the diameter of 15mm, and drying for 12 hours in a vacuum drying oven at 50 ℃ to obtain the black phosphorus alkene-MXene composite membrane.
The stability of the black phosphorus alkene-MXene composite membrane and the black phosphorus alkene membrane is verified:
and (3) placing the black phosphorus alkene film and the black phosphorus alkene-MXene composite film in the air, and observing the degradation condition of the black phosphorus alkene film and the black phosphorus alkene-MXene composite film. The degradation pattern is shown in FIG. 5.
BP-1 represents the topography of the black phospholene film after 1 month, MXene/BP-3 represents the topography of the composite film after 3 months, and the other same principles are carried out.
The experimental results are as follows: after the black phosphorus alkene membrane is placed for 1 month under the air environment condition, the black phosphorus alkene membrane gradually starts to absorb water and oxidize, after the black phosphorus alkene membrane is placed for 3 months, the black phosphorus alkene membrane is not kept complete any more, the edge part of the black phosphorus alkene membrane is partially oxidized, and after the black phosphorus alkene membrane is placed for 15 months, the black phosphorus alkene membrane is completely oxidized and degraded; compared with a pure black phosphorus alkene film, the black phosphorus alkene-MXene composite film is not obviously oxidized after being placed for 3 months under the air environment condition, and the composite film begins to be gradually oxidized after being placed for 5 months.
And (4) conclusion: the degradation rate of the black phosphorus alkene film is obviously faster than that of the composite material film, which shows that the stability of the black phosphorus alkene film is obviously improved after the black phosphorus alkene is compounded with MXene, and the black phosphorus alkene film is far better than that of the black phosphorus alkene film.
Example 5
The black phosphorus alkene-MXene composite membrane is used for separating H-containing substances2The mixed gas has good stability, avoids the possible degradation of pure black phosphorus alkene, and has higher H2The permeation quantity and the high gas selectivity can inhibit the permeation quantity of gas molecules with larger kinetic diameters to be extremely low, and the purity of the separated hydrogen is higher; the black phosphorus alkene-MXene composite membrane is a self-supporting membrane, does not need any substrate, is simple in preparation process and low in energy consumption, and can greatly save cost in practical application.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. A preparation method of a black phosphorus alkene-MXene composite membrane is characterized by comprising the following steps:
step 1: electrochemically stripping the blocky black phosphorus in an organic solvent of organic salt to obtain fluffy black phosphorus;
step 2: mixing fluffy black phosphorus with the solution, performing ultrasonic treatment and centrifugal washing to obtain supernatant, namely the solution containing the black phosphorus alkene nanosheets, and performing freeze drying to obtain black phosphorus alkene powder;
step 3: mixing lithium salt with acid solution to obtain mixed solution; then three-dimensionally layered Ti3AlC2Adding the powder into the mixed solution, uniformly stirring, centrifugally washing, and freeze-drying to obtain MXene powder;
step 4: adding the black phosphorus alkene powder obtained in Step2 and MXene powder obtained in Step3 into a brown reagent bottle according to the mass percentage of 1:1, ultrasonically mixing, stacking the compounded dispersion liquid on a substrate through a nano sheet self-assembly technology, and drying to obtain the black phosphorus alkene-MXene composite membrane.
2. The method for preparing the black phosphorus alkene-MXene composite membrane according to claim 1, wherein: the organic salt in Step1 is one of tetrabutylammonium bromide and tetrabutylammonium tetrafluoroborate; the organic solvent is one of acetonitrile, N-Dimethylformamide (DMF) and N-methylpyrrolidone (NMP); the mass ratio of the black phosphorus to the organic salt is 1: 1.2; the mass volume ratio of the organic salt to the organic solvent is 1.2g to 20 ml; the electrochemical stripping adopts a direct-current stabilized power supply as a power supply; the voltage is 3-10V; the current is 1-15 mA.
3. The method for preparing the black phosphorus alkene-MXene composite membrane according to claim 1, wherein: the organic solvent in Step2 is one of N, N-Dimethylformamide (DMF) and N-methylpyrrolidone (NMP); the mass volume ratio of the black phosphorus to the organic solvent is 0.1g to 80 ml; the ultrasonic power is 300-500W; the ultrasonic time is 1-3 hours, and the ultrasonic temperature is 0-10 ℃; the rotating speed of the centrifugation is 3000-13000 rpm; centrifuging for 5-60 min; the washing is carried out for 3-10 times by using deionized water.
4. The method for preparing the black phosphorus alkene-MXene composite membrane according to claim 1, wherein: the lithium salt in Step3 is one of lithium chloride and lithium fluoride; the acid solution is one of hydrofluoric acid and hydrochloric acid; the mass volume ratio of the lithium salt to the acid solution is 1g (30-80) mL; the centrifugation speed is 3000-8000 rap/min.
5. The method for preparing the black phosphorus alkene-MXene composite membrane according to claim 1, wherein: the ultrasonic condition in Step4 is 120-300W, and the temperature is 10-20 ℃; the nano assembly technology is one of a spin coating method, a spraying method, a natural drying method and a vacuum filtration method; the substrate is an Anodic Aluminum Oxide (AAO) film substrate, the aperture is 200nm, and the diameter is 10-200 mm; the drying condition is one or more of drying in an air drying oven and vacuum drying; the drying temperature is 10-80 ℃: the drying time is 10-72 hours.
6. The application of the black phosphorus alkene-MXene composite film is characterized by comprising the following steps:
(1) putting the black phosphorus alkene-MXene composite membrane into a gas separation device, and then introducing mixed gas to be separated with different kinetic diameters into a feeding side;
(2) introducing a purge gas at the purge side;
(3) and (3) introducing the purge gas in the step (2) into a gas chromatograph for detection, so as to obtain the permeation amount and selectivity of different gases.
7. The use of the black phosphorus alkene-MXene composite membrane according to claim 6, wherein: the thickness of the black phosphorus alkene-MXene composite film is 1-3 μm; the mixed gas is hydrogen (H)20.29nm), carbon dioxide (CO)20.33nm), nitrogen (N)20.364nm), methane (CH)40.4nm), e.g. H2/CO2,H2/N2And H2/CH4One or more combinations thereof.
8. The use of the black phosphene-MXene composite membrane according to claim 6, wherein: the purge gas is argon; the flow of the purging gas is 10-1000 ml/min; the gas chromatography is Fuli GC970 II gas chromatography.
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| CN115672403A (en) * | 2022-10-26 | 2023-02-03 | 北京理工大学 | ZIF-67/PNs nano composite material and preparation method and application thereof |
| CN117594364A (en) * | 2024-01-18 | 2024-02-23 | 河南师范大学 | Preparation method and application of mechanical property enhanced black phosphazene/MXene piezoelectricity composite membrane electrode |
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| CN115672403A (en) * | 2022-10-26 | 2023-02-03 | 北京理工大学 | ZIF-67/PNs nano composite material and preparation method and application thereof |
| CN117594364A (en) * | 2024-01-18 | 2024-02-23 | 河南师范大学 | Preparation method and application of mechanical property enhanced black phosphazene/MXene piezoelectricity composite membrane electrode |
| CN117594364B (en) * | 2024-01-18 | 2024-03-22 | 河南师范大学 | Preparation method and application of mechanical property enhanced black phosphazene/MXene piezoelectricity composite membrane electrode |
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