CN112206832B - Bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane, preparation method thereof and application thereof in hydrogen production by water vapor - Google Patents
Bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane, preparation method thereof and application thereof in hydrogen production by water vapor Download PDFInfo
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- 229920000491 Polyphenylsulfone Polymers 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 239000012528 membrane Substances 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002121 nanofiber Substances 0.000 title claims abstract description 40
- 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 28
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- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 7
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000007146 photocatalysis Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 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
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 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
- 238000011049 filling Methods 0.000 claims description 2
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- 230000004907 flux Effects 0.000 abstract description 22
- 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 46
- 229920001601 polyetherimide Polymers 0.000 description 46
- 239000010408 film Substances 0.000 description 39
- 239000007789 gas Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 241001198704 Aurivillius Species 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 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 bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane, a preparation method thereof and application thereof in hydrogen production by water vapor, 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 obtain a composite film PPSU/PEI; adding a catalyst Bi into the composite film PPSU/PEI 2 MoO 6 Continuously reacting to obtain spinning solution; and (3) loading the spinning solution by using a syringe, and placing the spinning solution into an electrostatic spinning device for spinning to prepare the photocatalytic fiber membrane. The photocatalytic fiber membrane has stable water vapor flux and hydrogen production efficiency, and the average water vapor flux is 264.7+/-7.7L/m when the carrier gas flow is 50mL/min in the test time of 6 hours 2 h, the average hydrogen production rate is 1832.95 +/-502.3 mu mol/m 3 hrMPa。
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 hydrogen production by water vapor.
Background
With the development of economy, the use of energy sources by human beings is increased, a certain environmental pollution is caused, the quantity of traditional energy sources is limited, and the energy sources are exhausted in the last day. Therefore, the development of new energy and the treatment of ecological environment pollution are the precondition of economic sustainable development. The hydrogen energy is a high-efficiency clean energy, and the photocatalysis 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 disadvantage of larger band gap, which results in lower photocatalytic efficiency, so more photocatalysts with high photocatalytic activity are developed.
The research shows that the bismuth-based photocatalyst has better utilization rate of visible light and higher chemical stability. The general chemical formula of bismuth molybdate is Bi 2 O 3 ·nMoO 3 Wherein n is equal to 1,2,3, corresponding to 3 structures. Experiments show that alpha-Bi 2 MoO 6 Is a typical Aurivillius oxide, and has the advantages of proper forbidden band width, chemical stability and the like. gamma-Bi 2 MoO 6 Can absorb sunlight and has good photocatalytic activity. Bi alone 2 MoO 6 The carrier mobility is low, and the problems of difficult recovery, uneven dispersion and the like are also caused, so that the photocatalytic efficiency is reduced. The nanofiber membrane prepared by the electrostatic spinning technology has the advantages of high porosity, large specific surface area and the like. Polyphenylsulfone (PPSU) polymer is a hydrophobic material with excellent hydrolytic stability, high temperature vapor resistance and ultraviolet light resistance. Polyetherimide (PEI) is a hydrophilic material with excellent propertiesHigh performance polymers with different thermal and chemical stability, and the obtained fibers have excellent performance. The PPSU/PEI 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 invention aims to provide the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane which has good effect in the hydrogen production process of catalytic water vapor and repeated stability. The invention aims to provide a preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane, which adopts an electrostatic spinning technology to prepare a catalyst Bi 2 MoO 6 Loaded on a thin film PPSU/PEI. The invention also aims to solve the technical problem of providing the application of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane in hydrogen production by photocatalysis steam, wherein the average steam flux is 264.7+/-7.7L/m when the carrier gas flow is 50mL/min in the test time of 6 hours 2 h, the average hydrogen production rate is 1832.95 +/-502.3 mu mol/m 3 hrMPa。
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane comprises the steps of adding PPSU and PEI into a reactor, adding a mixed solvent of acetone and NMP (N-methylpyrrolidone), and stirring and reacting to obtain a composite film PPSU/PEI; adding a catalyst Bi into the composite film PPSU/PEI 2 MoO 6 Continuously reacting to obtain spinning solution; loading spinning solution into an electrostatic spinning device by using a syringe to spin, and obtaining the loaded Bi 2 MoO 6 Is a PPSU/PEI composite nanofiber membrane.
The preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane comprises the steps of 2 MoO 6 Comprises the following steps:
(1) Adding bismuth nitrate pentahydrate and sodium molybdate dihydrate into a reaction vessel, adding glycol solution, mixing uniformly, then filling into a high-pressure reaction vessel, and reacting for 18-22 h at 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, centrifugal washing is carried out, and then the mixture is put into an oven at 80 ℃ for drying;
(3) The dried product is placed in a muffle furnace for high-temperature calcination, the temperature is firstly increased to 110 ℃ at the speed of 5 ℃/h, the calcination is carried out for 1h at 110 ℃, the temperature is increased to 500 ℃, and the calcination is carried out for 3h for standby.
The preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane comprises the steps of 2 MoO 6 The addition amount of the catalyst is5 to 15 percent of the mass of the composite film PPSU/PEI.
The volume ratio of PEI to PPSU is 0.2:1-3.5:1.
According to the preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane, the volume ratio of acetone to NMP is 2:3.
The preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane comprises the steps of preparing a composite film, wherein the reaction temperature in the preparation of the composite film 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 bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane comprises the steps of adding a catalyst Bi into a composite film PPSU/PEI 2 MoO 6 Continuing the reaction for 0.5-1.5 hr.
In the preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane, in the electrostatic spinning process, the inner diameter of a needle is 0.52mm, the spinning voltage is 20kV, the collecting distance is 15cm, the injection rate is 1mL/h, the electrostatic spinning time is 7h, and the ambient temperature is 25 ℃ and the humidity is 40%.
Bi-loaded PPSU/PEI composite nanofiber membrane prepared by preparation method of bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane 2 MoO 6 Is a PPSU/PEI composite nanofiber membrane.
The application of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane in hydrogen production by photocatalysis of water vapor.
The beneficial effects are that: compared with the prior art, the invention has the advantages that:
(1) Bi is adopted in the invention 2 M O O 6 The load on the nanofiber can reduce the rapid recombination of photo-generated electron-hole pairs and increase the hydrogen yield, thereby improving the photocatalysis efficiency of the membrane. The composite nanofiber membrane prepared by using the electrostatic spinning technology has better catalyst dispersibility, smaller pressure drop, less dense fiber composition and more uniform reaction of water vapor with the catalyst, thereby improving the hydrogen production rate of catalytic water vapor and the hydrogen production amount of catalytic water vapor.
(2) The composite membrane obtained by adopting the electrostatic spinning technology has good effect in the hydrogen production process of catalytic water vapor, and the average water vapor flux is 264.7+/-7.7L/m when the carrier gas flow is 50mL/min in the test time of 6 hours 2 h, the average hydrogen production rate is 1832.95 +/-502.3 mu mol/m 3 hrMPa; and the composite film has repeated stability.
Drawings
FIG. 1 is Bi 2 MoO 6 SEM scans of the catalyst, wherein the magnification of fig. 1a is 10kX and the magnification of fig. 1b is 50kX;
FIG. 2 is a SEM scan of a PPSU/PEI film of different proportions, wherein FIG. 2a is a SEM of the film without PPSU addition, FIG. 2b is a SEM of the film with PEI: PPSU ratio 14:4, FIG. 2c is a SEM of the film with PEI: PPSU ratio 9:9, FIG. 2d is a SEM of the film with PEI: PPSU ratio 4:14, and FIG. 2e is a SEM of the film without PEI addition;
FIG. 3 shows the addition of 10% Bi 2 MoO 6 SEM scans of PPSU/PEI films; wherein fig. 3a is an SEM image of the composite film M6, fig. 3b is an SEM image of the composite film M7, fig. 3c is an SEM image of the composite film M8, fig. 3d is an SEM image of the composite film M9, and fig. 3e is an SEM image of the composite film M10;
FIG. 4 is a graph showing the amounts of PPSU/PEI/Bi for different proportions of catalyst 2 MoO 6 An SEM scan of the film, wherein fig. 4a is an SEM of M11, fig. 4b is an SEM of M8, and fig. 4c is an SEM of M12;
FIG. 5 is an ultraviolet spectrum of a material, wherein FIG. 5a is Bi 2 MoO 6 FIG. 5b is a UV spectrum of the composite films M6, M7, M8, M9 and M10;
FIG. 6 is a graph of membrane water vapor flux and gas production efficiency for different composite membranes, wherein FIG. 6a is a graph of membrane water vapor flux and gas production efficiency for composite membranes M6, M7, M8, M9, and M10, and FIG. 6b is a graph of membrane water vapor flux and gas production efficiency for composite membranes M8, M11, and M12;
fig. 7 is a graph of water vapor flux and gas production efficiency under different operation parameters, wherein fig. 7a is a graph of water vapor flux and gas production efficiency under different nitrogen flows, and fig. 7b is a graph of water vapor flux and gas production efficiency of the composite membrane M8 under different operation times.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
The microscopic morphology analysis of the composite film is carried out by adopting a scanning electron microscope of Japanese electron S-4700 model; the thermal stability of the film is analyzed by adopting a thermogravimetric analyzer; the membrane surface functional groups were analyzed using FTIR-ATR (Nicolet-iS 5 infrared spectrometer, thermo Scientific); the ultraviolet-visible absorption wavelength of the film is analyzed by a ultraviolet-visible spectrometer with the model number of U-7000 (HITACHI); the gas produced by photocatalytic hydrolysis is qualitatively and quantitatively analyzed by a GC-112A-TCD gas chromatograph.
Example 1
The preparation method of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane comprises the following steps:
(1) Preparation of catalyst Bi 2 MoO 6 : 0.0929g of Bi (NO) 3 ) 3 ·5H 2 O and 0.0504g of Na 2 MoO 4 · 2 H 2 O (molar ratio of Bi to Mo is 2:1) is respectively filled into a reaction vessel, 20mL of ethylene glycol solution is added, and after uniform mixing, the mixture is added into a high-pressure reaction vessel for reaction for 20 hours at 160 ℃; after the reaction is finished, centrifugally washing for three times, and then placing in an oven at 80 ℃ for drying; placing the dried product in a muffle furnace for high-temperature calcination at a speed of 5 ℃/hHeating to 110 ℃, calcining for 1h at 110 ℃, heating to 500 ℃ and calcining for 3h to prepare the catalyst Bi 2 MoO 6 Standby;
(2) Placing PEI and PPSU in a beaker, adding acetone and NMP, stirring to obtain mixed solution, placing the mixed solution at 60deg.C, reacting for 4hr, and reacting on a magnetic stirrer with rotation speed of 300 rmp. Preparing a composite film PPSU/PEI;
(3) After the reaction is finished, adding the catalyst Bi prepared in the step (1) into the composite film PPSU/PEI 2 MoO 6 Continuously reacting for 1hr to obtain spinning solution; 7mL of spinning solution is loaded by a syringe and placed in an electrostatic spinning device for spinning, and a cut copper net is paved on a receiver so as to receive the prepared nanofiber; during electrospinning, the needle inside 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 producing a load Bi 2 MoO 6 Is a PPSU/PEI composite nanofiber membrane. Wherein the load Bi 2 MoO 6 The amounts of the components of the PPSU/PEI composite nanofiber membrane are changed, and are shown in Table 1
TABLE 1 PPSU/PEI/Bi 2 MoO 6 Composite fiber membrane composition table
FIG. 1 is Bi 2 MoO 6 From FIG. 1a, it can be seen that Bi 2 MoO 6 The agglomeration phenomenon of the catalyst is obvious, the agglomeration area is inconsistent, and the uneven dispersion of substances is indicated; from FIG. 1b, bi can be seen 2 MoO 6 The powder is composed of nano-sheets with smooth surfaces and different sizes.
Fig. 2 is an SEM scan of PPSU/PEI films in different ratios, wherein fig. 2a, 2b, 2c, 2d, 2e are the ratios of PEI to PPSU of 18:0, 14:4, 9:9, 4, respectively: 14. 0:18. From fig. 2a, 2b to 2c, it is clear that the beading on the fiber surface of PPSU/PEI film gradually disappears, and the beading is generated because the concentration of the spinning solution is too low and the viscosity is too low. In fig. 2d the beading completely disappeared and the fiber surface was smooth, and as the PPSU concentration increased, beading and globular fibers appeared on the electrospun fiber surface and the fiber size was not uniform.
FIG. 3 shows the addition of 10% Bi 2 MoO 6 SEM scans of PPSU/PEI films of (1), wherein fig. 3a, 3b, 3c, 3d, 3e are the ratios of PEI to PPSU of 18:0, 14:4, 9:9, 4, respectively: 14. 0:18. It can be seen from fig. 3a that the concentration of the solution is low, so that obvious spindle-shaped beading exists on the surface of the fiber, and the catalyst is unevenly loaded on the fiber and has agglomeration phenomenon; as can be seen from fig. 3b and 3c, the beading on the fiber surface gradually disappears, and the fiber diameter tends to be uniform; as can be seen from fig. 3d, the fibers formed more round beads and the catalyst loading was not uniform. This is because the viscosity of the solution is too high, which results in too small a distance between molecules, intertwining, and uneven filament output; as can be seen from fig. 3e, the fiber surface had spindle-shaped beads with a non-uniform diameter size distribution with significant white floc loading. From a comparison of fig. 2 and 3, it was found that the addition of bismuth molybdate had an effect on the optimum ratio PPSU/PEI.
FIG. 4 is a graph showing the amounts of PPSU/PEI/Bi for different proportions of catalyst 2 MoO 6 SEM scan of film, M11 (FIG. 4 a), M8 (FIG. 4 b), M12 (FIG. 4 c) doped with Bi 2 MoO 6 The amounts of the catalyst were 5%, 10% and 15%, respectively. As can be seen from fig. 4a, there are a small number of beads on the fibers, and the catalyst supported on the surface of the fibers is not obvious, because the catalyst addition amount is too small; as can be seen from fig. 4b, the catalyst loading on the fiber surface is uniform, no beading occurs and the surface is smooth; as can be seen from FIG. 4c, the surface of the fiber has a large number of beading, the catalyst agglomeration phenomenon is obvious, and the fiber is staggered, because the excessive dosage of the catalyst leads to the excessively high concentration of the spinning solution and unstable filament output. Therefore 10% Bi is selected 2 MoO 6 The adding amount is the optimal adding amount.
FIG. 5 is an ultraviolet spectrum of a material, FIG. 5a is Bi 2 MoO 6 UV-Vis graph of (a). As can be seen from FIG. 5a, the maximum absorption edge of bismuth molybdate is 500nm, which can be determined according to the absorption wavelengthBi is known 2 MoO 6 Absorption can occur in the ultraviolet region and the visible light region, and the absorption effect of light in the ultraviolet region is best. Calculated out, bi 2 MoO 6 The forbidden band width of (2.70 eV) accords with Bi 2 MoO 6 Is a forbidden band width 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 catalyst can be added to increase the photocatalytic capability of the composite film and utilize sunlight in a larger range. The forbidden bandwidths of M6-M10 are calculated to be 3.20eV, 3.24eV, 3.18eV, 3.23eV and 3.93eV respectively. The smaller the forbidden bandwidth, the lower the energy required for exciting photoelectrons, and the strongest light energy absorption capacity in the visible light region.
Example 2
The composite film prepared in example 1 was subjected to membrane water vapor flux and hydrogen production rate tests, wherein the test method and test operation procedure were the same as the method for producing hydrogen by photocatalytic membrane hydrolysis (CN 110577189 a) of the invention patent application, and the hydrogen production apparatus was similar to that of the above patent application except that the three-necked flask 1 was replaced with a gasification chamber. The photocatalytic water hydrogen production reaction flow comprises the following steps:
(1) Preparing oxygen-free water for later use by using 200mL of distilled water;
(2) Checking whether the whole device works normally or not and whether the tightness is good or not;
(3) Preparing a 13cm multiplied by 8cm sample composite nanofiber membrane, putting the sample composite nanofiber membrane into a transparent flat filter, and checking the tightness after the sample composite nanofiber membrane is placed;
(4) Preparing the anaerobic water prepared in the step (1) before the reaction; and is connected with a peristaltic pump;
(5) Opening a valve of the high-purity nitrogen bottle, adjusting the flow rate, opening a mass flowmeter and setting to ensure that nitrogen flows normally in the device;
(6) Opening a switch of a heating coil, and regulating the temperature to 100 ℃;
(7) When the gasification chamber reaches a state of complete preheating, a peristaltic pump is started to regulate the flow speed to start reaction at 1mL/min, and whether the reading of a recorder is normal or not is checked;
(8) When the anaerobic water enters the gasification chamber, the anaerobic water is gasified into water vapor because the temperature of the gasification chamber is 100 ℃; under the pushing of nitrogen, water vapor enters the transparent flat filter through the heating coil; under the irradiation of an ultraviolet lamp, the water vapor entering the transparent flat filter tank generates hydrogen under the action of a catalyst on the sample composite nanofiber membrane;
(9) The hydrogen produced by photocatalysis comes out and enters a drying bottle for drying, and then enters an electronic soap bubble flowmeter for measuring the gas flow rate;
(10) After the indication of the electronic soap bubble flowmeter is stable, the sampling can be started, the collecting time of the gas collecting bag is 3min once, and the collected gas is detected and analyzed by a gas chromatograph.
The test formula of the membrane water vapor flux is as follows:
wherein: c is the water vapor flux of the membrane, L/m 2 H; v is the gas passing through every minute, L; a is the area of the film, m 2 The method comprises the steps of carrying out a first treatment on the surface of the T is the reaction time, h.
The test formula of the hydrogen production rate is:
wherein: y is hydrogen production rate, mu mol/(m) 3 hrMPa); a is sampling time of each time, and 3min; b is the pressure in sampling and MPa.
The results of the membrane water flux and hydrogen production rate tests of the composite nanofiber membrane are shown in fig. 6. As shown in fig. 6a, the water flux per unit area of M6 is maximum because PEI is a hydrophilic material; the water vapor flux and hydrogen production rate of M9 are both minimal, because of the obvious agglomeration phenomenon and the large number of round beads of the nanofibers; the hydrogen production rate of M8 is maximum and reaches 1167.94 mu mol/(M) 3 hrMPa) due to uniform distribution of photocatalyst supported on fiber surface and large specific surface area, therebyThe utilization rate of ultraviolet light is improved. As shown in fig. 6b, the hydrogen production rate decreases with the increase of the catalyst addition amount, because the too high doping ratio of the catalyst may easily cause the occurrence of agglomeration phenomenon, thereby being disadvantageous for the photocatalytic reaction. Considering that the catalyst addition amount is too low, insufficient catalyst loading on the membrane may result; too high a level may be detrimental to the reaction, and the light absorption of M8 is optimal among the three. Comprehensively considering that the doping amount of the catalyst is 10 percent, the optimal adding amount is selected.
FIG. 7 is a graph of water gas flux and gas production efficiency at various operating parameters. Fig. 7a is a graph of the effect of carrier gas flow on film properties. As can be seen from FIG. 7a, at a test time of 6 hours, the average water vapor flux was 264.7.+ -. 7.7, 563.2.+ -. 41.6 and 1194.8.+ -. 43.7L/m for carrier gas flows of 50, 100 and 200mL/min 2 h, the average hydrogen production rate is 2201.34 +/-448.47, 1167.94 +/-774.97 and 735.07 +/-497.50 mu mol/m respectively 3 hrMPa. The trend of the water vapor flux per unit area is opposite to the hydrogen production rate, because the larger the nitrogen flow, the shorter the residence time of the water vapor on the film, resulting in a larger water vapor flux, and the faster the water vapor flux will result in a shorter contact time with the catalyst, resulting in a smaller hydrogen production rate.
As can be seen from fig. 7b, the water flux was relatively stable at different carrier gas flows. In addition, when the reaction time is 30min, the effect of hydrogen production rate is optimal, the subsequent slow decline of the hydrogen production rate is realized, and a great amount of water gas adheres to the surface of the catalyst along with the time to reduce the reduction efficiency, but the water gas on the surface of the catalyst can be slowly evaporated and slowly recovered about 180 min because of the reaction under the high-temperature environment (-100 ℃), so that the circulation is kept.
After long-time testing, the hydrogen production amount generated by the film has periodic periodicity, which shows that the catalytic fiber film has optical stability and reusability under the irradiation of high-temperature ultraviolet light environment.
Claims (6)
1. The application of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane in hydrogen production by photocatalysis of water vapor is characterized in that the bismuth molybdate-loaded PPSU/PEI composite nanofiber membraneAdding PPSU and PEI into a reactor, adding a mixed solvent of acetone and NMP, and stirring for reaction to obtain a composite film PPSU/PEI; adding a catalyst Bi into the composite film PPSU/PEI 2 MoO 6 Continuously reacting to obtain spinning solution; loading spinning solution into an electrostatic spinning device by using a syringe to spin, and obtaining the loaded Bi 2 MoO 6 The PPSU/PEI composite nanofiber membrane;
the catalyst Bi 2 MoO 6 The addition amount of the catalyst is 5% -15% of the mass of the composite film PPSU/PEI;
in the electrostatic spinning process, the inner diameter of a needle is 0.52 and mm, the spinning voltage is 20kV, the collecting 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%.
2. The application of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane in photocatalytic water vapor hydrogen production according to claim 1, characterized in that the catalyst Bi 2 MoO 6 Comprises the following steps:
(1) Adding bismuth nitrate pentahydrate and sodium molybdate dihydrate into a reaction vessel, adding an ethylene glycol solution, uniformly mixing, and then filling into a high-pressure reaction vessel for reaction for 18-22 h at 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, centrifugal washing is carried out, and then the mixture is put into an oven at 80 ℃ for drying;
(3) The dried product is placed in a muffle furnace for high-temperature calcination, the temperature is firstly increased to 110 ℃ at the speed of 5 ℃/h, the calcination is carried out at 110 ℃ for 1h, the temperature is increased to 500 ℃, and the calcination is carried out for 3h for standby.
3. The application of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane in photocatalytic water vapor hydrogen production, which is characterized in that the volume ratio of PEI to PPSU is 0.2:1-3.5:1.
4. The use of bismuth molybdate loaded PPSU/PEI composite nanofiber membrane according to claim 1 for photocatalytic water vapor hydrogen production, wherein the volume ratio of acetone to NMP is 2:3.
5. The application of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane in hydrogen production by photocatalysis of water vapor, which is characterized in that the reaction temperature in the preparation of the composite film PPSU/PEI is 40-80 ℃, the reaction time is 3-5 hr, and the rotating speed of a magnetic stirrer is 200-400 rpm.
6. The application of the bismuth molybdate-loaded PPSU/PEI composite nanofiber membrane in hydrogen production by photocatalysis of water vapor, wherein a catalyst Bi is added into a composite film PPSU/PEI 2 MoO 6 Continuing the reaction for 0.5-1.5 hr.
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| CN104192907A (en) * | 2014-08-21 | 2014-12-10 | 齐鲁工业大学 | Preparation method of gamma-bismuth molybdate nanotubes |
| CN106964407A (en) * | 2017-03-28 | 2017-07-21 | 齐鲁工业大学 | A kind of CuPc/γ bismuth molybdate composite nano fiber catalysis materials and preparation method and application |
| CN110577189A (en) * | 2019-09-20 | 2019-12-17 | 武夷学院 | Method for producing hydrogen by photocatalytic membrane hydrolysis |
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| CN104192907A (en) * | 2014-08-21 | 2014-12-10 | 齐鲁工业大学 | Preparation method of gamma-bismuth molybdate nanotubes |
| CN106964407A (en) * | 2017-03-28 | 2017-07-21 | 齐鲁工业大学 | A kind of CuPc/γ bismuth molybdate composite nano fiber catalysis materials and preparation method and application |
| CN110577189A (en) * | 2019-09-20 | 2019-12-17 | 武夷学院 | Method for producing hydrogen by photocatalytic membrane hydrolysis |
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