CN112206832A - PPSU/PEI composite nanofiber membrane loaded with bismuth molybdate, preparation method thereof and application thereof in steam hydrogen production - Google Patents
PPSU/PEI composite nanofiber membrane loaded with bismuth molybdate, preparation method thereof and application thereof in steam hydrogen production Download PDFInfo
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- 229920000491 Polyphenylsulfone Polymers 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000012528 membrane Substances 0.000 title claims abstract description 63
- 239000002121 nanofiber Substances 0.000 title claims abstract description 47
- 239000001257 hydrogen Substances 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
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- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- 229910002900 Bi2MoO6 Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 abstract description 22
- 230000004907 flux Effects 0.000 abstract description 22
- 239000007789 gas Substances 0.000 abstract description 20
- 238000012360 testing method Methods 0.000 abstract description 10
- 239000012159 carrier gas Substances 0.000 abstract description 6
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 239000004697 Polyetherimide Substances 0.000 description 50
- 229920001601 polyetherimide Polymers 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 239000010408 film Substances 0.000 description 32
- 239000011324 bead Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
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- 238000002309 gasification Methods 0.000 description 3
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- 230000031700 light absorption Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical group O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- 241001198704 Aurivillius Species 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
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a PPSU/PEI composite nanofiber membrane loaded with bismuth molybdate, a preparation method thereof and application thereof in steam hydrogen production, and belongs to the technical field of photocatalyst preparation. Adding PPSU and PEI into a reactor, adding a mixed solvent of acetone and NMP, and stirring for reaction to prepare a composite film PPSU/PEI; adding catalyst Bi into composite film PPSU/PEI2MoO6Continuously reacting to prepare spinning solution; and (3) putting the spinning solution loaded by an injector into an electrostatic spinning device for spinning to obtain the photocatalytic fiber membrane. The photocatalytic fiber membrane has stable water-gas flux and hydrogen production efficiency, and the average water-gas flux is 264.7 +/-7.7L/m when the test time of 6 hours and the carrier gas flow are 50mL/min2h, the average hydrogen production rate is 1832.95 +/-502.3 mu mol/m3hrMPa。
Description
Technical Field
The invention belongs to the technical field of photocatalyst preparation, and particularly relates to a bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane, a preparation method thereof and application thereof in steam hydrogen production.
Background
With the development of economy, the use of energy resources by human beings is increased, certain environmental pollution is caused, the quantity of traditional energy resources is limited, and the energy resources are exhausted in the whole day. Therefore, the development of new energy and the treatment of ecological environmental pollution are the premise of economic sustainable development. The hydrogen energy is a high-efficiency clean energy, and the photocatalytic hydrogen production technology initiated by Fujishima and the like has the advantages of stable reaction, low cost and the like, and becomes a novel hydrogen production technology with development potential. The semiconductor material selected before has the defect of larger band gap, so that the photocatalysis efficiency is lower, and more photocatalysts with high photocatalytic activity are developed.
Researches find that the bismuth-based photocatalyst has better utilization rate of visible light and higher chemical stability. The general chemical formula of bismuth molybdate is Bi2O3·nMoO3Where n is equal to 1, 2, 3, corresponding to 3 structures. Experiments show that the alpha-Bi2MoO6Is a typical oneThe Aurivillius oxide has the advantages of proper forbidden band width, chemical stability and the like. gamma-Bi2MoO6Can absorb sunlight and has good photocatalytic activity. Use of Bi alone2MoO6The carrier mobility is low, and there are problems of difficulty in recovery, non-uniform dispersion, etc., thereby decreasing the photocatalytic efficiency. The nanofiber membrane prepared by the electrostatic spinning technology has the advantages of high porosity, large specific surface area and the like. The polyphenylsulfone (PPSU) polymer is a hydrophobic material, and has excellent performances of hydrolytic stability, high-temperature water vapor resistance and ultraviolet light resistance. Polyetherimide (PEI) is a hydrophilic material, a high-performance polymer with excellent thermal stability and chemical stability, and the obtained fiber has excellent performance. The PPSU/PEI thin film prepared by blending the two materials has excellent heat resistance, high-temperature steam resistance and ultraviolet light resistance, and can stably react under the condition of hydrogen production by steam hydrolysis.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane, the composite nanofiber membrane has a good effect in the process of catalyzing water vapor to produce hydrogen, and the composite nanofiber membrane has repeated stability. The invention aims to solve another technical problem of providing a preparation method of a PPSU/PEI composite nanofiber membrane loaded with bismuth molybdate, wherein the preparation method adopts an electrostatic spinning technology and uses a catalyst Bi2MoO6Loaded on a thin film PPSU/PEI. The invention also aims to solve the technical problem of providing an application of the PPSU/PEI composite nanofiber membrane loaded with bismuth molybdate in photocatalytic steam hydrogen production, wherein the average water vapor flux is 264.7 +/-7.7L/m when the test time is 6 hours and the carrier gas flow is 50mL/min2h, the average hydrogen production rate is 1832.95 +/-502.3 mu mol/m3hrMPa。
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a PPSU/PEI composite nanofiber membrane loaded with bismuth molybdate comprises the steps of mixing PPSU and PEIAdding PEI into a reactor, adding a mixed solvent of acetone and NMP (N-methylpyrrolidone), and stirring for reaction to obtain a composite film PPSU/PEI; adding catalyst Bi into composite film PPSU/PEI2MoO6Continuously reacting to prepare spinning solution; the spinning solution is loaded by an injector and is placed in an electrostatic spinning device for spinning to prepare the loaded Bi2MoO6The PPSU/PEI composite nanofiber membrane.
The preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane comprises the step of preparing the catalyst Bi2MoO6The preparation method comprises the following steps:
(1) adding bismuth nitrate pentahydrate and sodium molybdate dihydrate into a reaction vessel, adding an ethylene glycol solution, uniformly mixing, putting into a high-pressure reaction kettle, and reacting for 18-22 h at the temperature of 140-180 ℃; the molar ratio of the bismuth nitrate pentahydrate to the sodium molybdate dihydrate is 1: 1-3: 1;
(2) after the reaction is finished, carrying out centrifugal washing, and then drying in an oven at 80 ℃;
(3) and placing the dried product in a muffle furnace for high-temperature calcination, heating to 110 ℃ at the speed of 5 ℃/h, calcining for 1h at 110 ℃, heating to 500 ℃ and calcining for 3h for later use.
The preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane comprises the step of preparing the catalyst Bi2MoO6The addition amount of the composite film is 5-15% of the mass of the PPSU/PEI.
According to the preparation method of the PPSU/PEI composite nanofiber membrane loaded with the bismuth molybdate, the volume ratio of PEI to PPSU is 0.2: 1-3.5: 1.
According to the preparation method of the PPSU/PEI composite nanofiber membrane loaded with the bismuth molybdate, the volume ratio of acetone to NMP is 2: 3.
According to the preparation method of the PPSU/PEI composite nanofiber membrane loaded with the bismuth molybdate, the reaction temperature in the preparation of the composite membrane PPSU/PEI is 40-80 ℃, the reaction time is 3-5 hr, and the rotating speed of a magnetic stirrer is 200-400 rmp.
The preparation method of the PPSU/PEI composite nanofiber membrane loaded with bismuth molybdate comprises the step of adding a catalyst Bi into a composite thin film PPSU/PEI2MoO6The reaction is continued for 0.5 to 1.5 hr.
According to the preparation method of the PPSU/PEI composite nanofiber membrane loaded with the bismuth molybdate, in the electrostatic spinning process, the inner diameter of a needle is 0.52mm, the spinning voltage is 20kV, the collection distance is 15cm, the injection rate is 1mL/h, the electrostatic spinning time is 7h, the ambient temperature is 25 ℃, and the humidity is 40%.
The Bi-loaded PPSU/PEI composite nanofiber membrane prepared by the preparation method2MoO6The PPSU/PEI composite nanofiber membrane.
The PPSU/PEI composite nanofiber membrane loaded with the bismuth molybdate is applied to photocatalytic water vapor hydrogen production.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) in the invention, Bi2MOO6The nano-fiber can reduce the rapid recombination of photo-generated electron-hole pairs and increase the hydrogen yield, thereby improving the photocatalytic efficiency of the membrane. The composite nanofiber membrane prepared by the electrostatic spinning technology has better catalyst dispersibility, smaller pressure drop and less compact fiber composition, and the water vapor can uniformly react with the catalyst, so that the hydrogen production rate by catalyzing the water vapor and the hydrogen production amount by catalyzing the water vapor are improved.
(2) The composite membrane obtained by adopting the electrostatic spinning technology has good effect in the process of catalyzing water vapor to produce hydrogen, and the average water vapor flux is 264.7 +/-7.7L/m when the flow of carrier gas is 50mL/min within 6 hours of test time2h, the average hydrogen production rate is 1832.95 +/-502.3 mu mol/m3hrMPa; and the composite membrane has repeated stability.
Drawings
FIG. 1 shows Bi2MoO6SEM scan of the catalyst, wherein the magnification of fig. 1a is 10kX and the magnification of fig. 1b is 50 kX;
FIG. 2 is SEM scanning of PPSU/PEI films at different ratios, wherein FIG. 2a is SEM of the film without the addition of PPSU, FIG. 2b is SEM of the film at 14:4 PEI: PPSU ratio, FIG. 2c is SEM of the film at 9:9 PEI: PPSU ratio, FIG. 2d is SEM of the film at 4:14 PEI: PPSU ratio, and FIG. 2e is SEM of the film without the addition of PEI;
FIG. 3 shows the addition of 10% Bi2MoO6SEM scan of the PPSU/PEI thin film of (1); wherein FIG. 3a is an SEM image of composite film M6, FIG. 3b is an SEM image of composite film M7, FIG. 3c is an SEM image of composite film M8, FIG. 3d is an SEM image of composite film M9, and FIG. 3e is an SEM image of composite film M10;
FIG. 4 shows the amounts of PPSU/PEI/Bi in different ratios of catalyst2MoO6SEM scanning of the thin film, wherein fig. 4a is SEM of M11, fig. 4b is SEM of M8, and fig. 4c is SEM of M12;
FIG. 5 is a UV spectrum of a material, wherein FIG. 5a is Bi2MoO6FIG. 5b is a UV spectrum of composite films M6, M7, M8, M9 and M10;
FIG. 6 is a graph of water vapor flux and gas production efficiency of different composite films, wherein FIG. 6a is a graph of water vapor flux and gas production efficiency of composite films M6, M7, M8, M9 and M10, and FIG. 6b is a graph of water vapor flux and gas production efficiency of composite films M8, M11 and M12;
FIG. 7 is a graph of water vapor flux and gas production efficiency under different operating parameters, wherein FIG. 7a is a graph of water vapor flux and gas production efficiency under different nitrogen flow rates, and FIG. 7b is a graph of water vapor flux and gas production efficiency of composite film M8 under different operating times.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
The microscopic morphology analysis of the composite film is observed by adopting a scanning electron microscope of Japanese electron S-4700 model; the thermal stability of the membrane was analyzed using a thermogravimetric analyzer; the membrane surface functional groups were analyzed by FTIR-ATR (Nicolet-iS5 Infrared Spectroscopy, Thermo Scientific); analyzing the ultraviolet-visible absorption wavelength of the film by using an ultraviolet-visible spectrometer with the model number of U-7000 (HITACHI); the gas for producing hydrogen by photocatalytic hydrolysis is qualitatively and quantitatively analyzed by a gas chromatograph with the model of GC-112A-TCD.
Example 1
The preparation method of the PPSU/PEI composite nanofiber membrane loaded with bismuth molybdate comprises the following steps:
(1) preparation of catalyst Bi2MoO6: weighing 0.0929g of Bi (NO)3)3·5H2O and 0.0504g of Na2MoO4·2H2O (the molar ratio of Bi to Mo is 2:1) is respectively filled into a reaction container, 20mL of glycol solution is added, the mixture is uniformly mixed and then is added into a high-pressure reaction kettle, and the mixture is reacted for 20 hours at the temperature of 160 ℃; after the reaction is finished, centrifugally washing for three times, and then drying in an oven at 80 ℃; placing the dried product in a muffle furnace for high-temperature calcination, firstly heating to 110 ℃ at the speed of 5 ℃/h, calcining for 1h at 110 ℃, then heating to 500 ℃, and calcining for 3h to prepare the catalyst Bi2MoO6And is ready for use;
(2) putting PEI and PPSU in a beaker, adding acetone and NMP, stirring to obtain a mixed solution, and reacting the mixed solution on a magnetic stirrer at the temperature of 60 ℃ and the rotating speed of 300rmp for 4 hr. Preparing a composite film PPSU/PEI;
(3) adding the catalyst Bi prepared in the step (1) into the composite film PPSU/PEI after the reaction is finished2MoO6Continuing to react for 1hr to obtain spinning solution; 7mL of spinning solution is loaded and taken by an injector and is placed in an electrostatic spinning device for spinning, and a cut copper net is laid on a receiver so as to receive the prepared nano fibers; in the electrospinning process, the needle inner diameter, spinning voltage, collection distance, injection rate, electrospinning time, ambient temperature and humidity were 0.52mm, 20kV, 15cm, 1mL/h, 7h, 25 ℃ and 40%, respectively. Thereby obtaining the supported Bi2MoO6The PPSU/PEI composite nanofiber membrane. Wherein, Bi is loaded2MoO6The dosage of the components of the PPSU/PEI composite nanofiber membrane is changed, and is specifically shown in Table 1
TABLE 1 PPSU/PEI/Bi2MoO6Composite fiber film composition table
FIG. 1 shows Bi2MoO6From FIG. 1a, Bi is shown2MoO6The catalyst agglomeration phenomenon is obvious, and the agglomerated areas are also inconsistent in size, which indicates that the material is not uniformly dispersed; from FIG. 1b, Bi can be seen2MoO6The powder consists of nano sheets with smooth surfaces and different sizes.
FIG. 2 is SEM scan of PPSU/PEI thin film in different ratios, wherein FIG. 2a, FIG. 2b, FIG. 2c, FIG. 2d, FIG. 2e shows the ratios of PEI to PPSU are 18:0, 14:4, 9:9, 4: 14. 0: 18. As is clear from fig. 2a, 2b to 2c, the reason why the fiber surface of the PPSU/PEI film had gradually lost the bead structure and the bead structure was generated was that the spinning solution had too low a concentration and a viscosity was too low. In FIG. 2d, the beads are completely disappeared and the fiber surface is smooth, and as the concentration of PPSU is increased, the bead and spherical fibers appear on the surface of the electrospun fiber, and the fiber size is not uniform.
FIG. 3 shows the addition of 10% Bi2MoO6The SEM scanning images of the PPSU/PEI thin film of (1), wherein the ratios of PEI to PPSU in FIG. 3a, FIG. 3b, FIG. 3c, FIG. 3d and FIG. 3e are 18:0, 14:4, 9:9 and 4 respectively: 14. 0: 18. As can be seen from fig. 3a, due to the low concentration of the solution, the fiber surface has obvious spindle-shaped beads, and the catalyst is loaded on the fiber unevenly and has agglomeration phenomenon; as can be seen from fig. 3b and 3c, the bead on the surface of the fiber gradually disappears, and the fiber diameter tends to be uniform; as can be seen from fig. 3d, the fibers form more round beads and the catalyst loading is not uniform. The reason is that the solution has overlarge viscosity, so that the distance between molecules is too small, the molecules are mutually wound, and the filament is not uniformly discharged; as can be seen from fig. 3e, the fiber surface has spindle-shaped beads, and the white floc load is evident due to the uneven diameter distribution. From a comparison of FIG. 2 with FIG. 3, it was found that the addition of bismuth molybdate had an effect on the optimal ratio of PPSU/PEI.
FIG. 4 shows the amounts of PPSU/PEI/Bi in different ratios of catalyst2MoO6SEM scanning of the films, M11 (FIG. 4a), M8 (FIG. 4b), M12 (FIG. 4c) doped with Bi2MoO6The amounts of catalyst were 5%, 10%, 15%, respectively. As can be seen from FIG. 4a, there are a few beads on the fiberThe catalyst supported on the surface of the fiber is not obvious, because the adding amount of the catalyst is too small; as can be seen from fig. 4b, the catalyst loading on the fiber surface was uniform, no bead formation occurred and the surface was smooth; as can be seen from FIG. 4c, there are a lot of beads on the surface of the fiber, the catalyst agglomeration phenomenon is obvious, and the fiber is disordered and staggered, because the concentration of the spinning solution is too high due to the excessive catalyst addition, and the filament output is not stable. Therefore, 10% Bi is selected2MoO6The adding amount is the optimal adding amount.
FIG. 5 is a UV spectrum of the material, and FIG. 5a is Bi2MoO6UV-Vis diagram of (1). As can be seen from FIG. 5a, the maximum absorption edge of bismuth molybdate is 500nm, and Bi is known from the absorption wavelength2MoO6Absorption occurs in both the ultraviolet region and the visible region, and the effect of light absorption in the ultraviolet region is most excellent. Calculated to obtain Bi2MoO6Has a forbidden band width of 2.70eV in accordance with Bi2MoO6The forbidden bandwidth range of (a). As shown in fig. 5b, the film has stronger light absorption in the uv region relative to the uv spectrum of pure bismuth molybdate; the addition of the catalyst can increase the photocatalytic capability of the composite membrane and greatly utilize sunlight. The forbidden band widths of M6-M10 are respectively 3.20eV, 3.24eV, 3.18eV, 3.23eV and 3.93 eV. The smaller the forbidden band width, the lower the energy required for exciting photoelectrons, and the strongest light energy absorption capability in the visible light region.
Example 2
The composite film prepared in example 1 was subjected to membrane water-gas flux and hydrogen production rate tests, wherein the test method and test operation were the same as the method of photocatalytic membrane hydrolysis for hydrogen production (CN110577189A), and the apparatus for hydrogen production was similar to that of the above patent application except that the three-neck flask 1 was replaced with a vaporizer. The reaction process for preparing hydrogen by photocatalytic water comprises the following steps:
(1) preparing oxygen-free water by using 200mL of distilled water for later use;
(2) checking whether the whole set of device works normally and whether the sealing performance is good;
(3) preparing a sample composite nanofiber membrane of 13cm multiplied by 8cm, putting the sample composite nanofiber membrane into a transparent flat plate filter, and checking the sealing property after the sample composite nanofiber membrane is placed;
(4) preparing the oxygen-free water prepared in the step (1) before reaction; and is connected with a peristaltic pump;
(5) opening a valve of a high-purity nitrogen cylinder, adjusting the flow rate, opening a mass flowmeter and setting to ensure that nitrogen flows normally in the device;
(6) turning on a switch of the heating coil, and adjusting the temperature of the heating coil to 100 ℃;
(7) when the gasification chamber reaches the state of complete preheating, a peristaltic pump is started to adjust the flow speed to start reaction at 1mL/min, and whether the reading of a recorder is normal is checked;
(8) when the oxygen-free water enters the gasification chamber, the oxygen-free water is gasified into water vapor because the temperature of the gasification chamber is 100 ℃; under the push of nitrogen, water vapor enters the transparent flat plate filter through the heating coil; under the irradiation of an ultraviolet lamp, the water vapor entering the transparent flat plate filter generates hydrogen under the action of a catalyst on the sample composite nanofiber membrane;
(9) hydrogen prepared by photocatalysis is discharged and then enters a drying bottle for drying, and then enters an electronic soap bubble flowmeter to measure the gas flow rate;
(10) and after the reading of the electronic soap bubble flowmeter is stable, the sampling can be started, the acquisition time of the gas collection bag is 3min, and the acquired gas is detected and analyzed by a gas chromatograph.
The test formula of the membrane water vapor flux is as follows:
in the formula: c is the water-gas flux of the membrane, L/m2H; v is the gas passing per minute, L; a is the area of the film, m2(ii) a T is the reaction time, h.
The test formula of the hydrogen production rate is as follows:
in the formula: y is hydrogen production rate, mu mol/(m)3hrMPa); a is sampling time of each time, 3 min; and B is the pressure during sampling, MPa.
The results of the membrane water-gas flux and hydrogen production rate tests of the composite nanofiber membrane are shown in fig. 6. As shown in fig. 6a, the moisture flux per unit area of M6 was greatest because PEI is a hydrophilic material; the water vapor flux and the hydrogen production rate of M9 are both minimal because of the obvious agglomeration phenomenon and a large number of round beads of the nano fibers; the hydrogen production rate of M8 is the maximum, and reaches 1167.94 mu mol/(M)3hrMPa), because the photocatalyst loaded on the surface of the fiber is uniformly distributed and has large specific surface area, the utilization rate of ultraviolet light is improved. As shown in fig. 6b, the hydrogen production rate decreases with the increase of the catalyst dosage, because the doping ratio of the catalyst is too high, which easily causes the agglomeration phenomenon, thus being not beneficial to the photocatalytic reaction. Considering that when the dosage of the catalyst is too low, the loading amount of the catalyst on the membrane is possibly insufficient; too high a level will adversely affect the reaction and the light absorption of M8 is optimal among the three. Comprehensively considering, the doping amount of the catalyst is selected to be 10% as the optimal addition amount.
FIG. 7 is a graph of water vapor flux and gas production efficiency under different operating parameters. FIG. 7a is a graph that illustrates the effect of carrier gas flow on film properties. As can be seen in FIG. 7a, the mean water vapor flux was 264.7. + -. 7.7, 563.2. + -. 41.6 and 1194.8. + -. 43.7L/m at 6 hours of test time with carrier gas flow rates of 50, 100 and 200mL/min2h, the average hydrogen production rate is 2201.34 +/-448.47, 1167.94 +/-774.97 and 735.07 +/-497.50 mu mol/m3hrMPa. The trend of change of the water vapor flux per unit area is opposite to the hydrogen production rate, because the larger the nitrogen flow is, the shorter the residence time of the water vapor on the membrane is, so that the water vapor flux is larger, and the too fast water vapor flux can cause the contact time with the catalyst to be shorter, so that the hydrogen production rate is smaller.
As can be seen from fig. 7b, the flux of water and gas is stable for different carrier gas flow rates. In addition, when the reaction time is 30min, the hydrogen production rate effect is optimal, the subsequent reaction time is gradually reduced, a large amount of water vapor adheres to the surface of the catalyst along with the time, so that the reduction efficiency is reduced, but the water vapor on the surface of the catalyst is slowly evaporated because of the reaction in a high-temperature environment (about 100 ℃), the hydrogen production rate is slowly recovered about 180 minutes, and the circulation is kept all the time.
After long-time testing, the hydrogen yield generated by the film has periodic cyclicity, which shows that the catalytic fiber film has optical stability and reusability under the irradiation of high-temperature ultraviolet light environment.
Claims (10)
1. A preparation method of a PPSU/PEI composite nanofiber membrane loaded with bismuth molybdate is characterized in that the PPSU and PEI are added into a reactor, a mixed solvent of acetone and NMP is added, and stirring reaction is carried out to prepare a composite membrane PPSU/PEI; adding catalyst Bi into composite film PPSU/PEI2MoO6Continuously reacting to prepare spinning solution; the spinning solution is loaded by an injector and is placed in an electrostatic spinning device for spinning to prepare the loaded Bi2MoO6The PPSU/PEI composite nanofiber membrane.
2. The method for preparing the PPSU/PEI composite nanofiber membrane supporting the bismuth molybdate as claimed in claim 1, wherein the catalyst Bi2MoO6The preparation method comprises the following steps:
(1) adding bismuth nitrate pentahydrate and sodium molybdate dihydrate into a reaction vessel, adding an ethylene glycol solution, uniformly mixing, putting into a high-pressure reaction kettle, and reacting for 18-22 h at the temperature of 140-180 ℃; the molar ratio of the bismuth nitrate pentahydrate to the sodium molybdate dihydrate is 1: 1-3: 1;
(2) after the reaction is finished, carrying out centrifugal washing, and then drying in an oven at 80 ℃;
(3) and placing the dried product in a muffle furnace for high-temperature calcination, heating to 110 ℃ at the speed of 5 ℃/h, calcining for 1h at 110 ℃, heating to 500 ℃ and calcining for 3h for later use.
3. The method for preparing the PPSU/PEI composite nanofiber membrane supporting the bismuth molybdate as claimed in claim 1, wherein the catalyst Bi2MoO6The addition amount of the composite film is 5-15% of the mass of the PPSU/PEI.
4. The preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane as claimed in claim 1, wherein the volume ratio of PEI to PPSU is 0.2: 1-3.5: 1.
5. The method for preparing the PPSU/PEI composite nanofiber membrane loaded with the bismuth molybdate as claimed in claim 1, wherein the volume ratio of acetone to NMP is 2: 3.
6. The method for preparing the PPSU/PEI composite nanofiber membrane loaded with the bismuth molybdate according to claim 1, wherein the reaction temperature in the preparation of the composite thin membrane PPSU/PEI is 40-80 ℃, the reaction time is 3-5 hr, and the rotation speed of a magnetic stirrer is 200-400 rmp.
7. The method for preparing the PPSU/PEI composite nanofiber membrane loaded with the bismuth molybdate according to claim 1, wherein a catalyst Bi is added into the PPSU/PEI composite thin membrane2MoO6The reaction is continued for 0.5 to 1.5 hr.
8. The method for preparing the PPSU/PEI composite nanofiber membrane loaded with the bismuth molybdate according to claim 1, wherein in the electrostatic spinning process, the inner diameter of a needle is 0.52mm, the spinning voltage is 20kV, the collection distance is 15cm, the injection rate is 1mL/h, the electrostatic spinning time is 7h, the ambient temperature is 25 ℃, and the humidity is 40%.
9. Bi-loaded PPSU/PEI composite nanofiber membrane prepared by using method for preparing bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane as claimed in any one of claims 1-82MoO6The PPSU/PEI composite nanofiber membrane.
10. The use of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane of claim 9 in photocatalytic hydrogen production by steam.
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