AU2021102854A4 - A bismuth molybdate/carbon flexible membrane photocatalytic material, preparation method and application thereof - Google Patents
A bismuth molybdate/carbon flexible membrane photocatalytic material, preparation method and application thereof Download PDFInfo
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- bismuth
- bismuth molybdate
- carbon
- flexible membrane
- molybdate
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- 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 122
- 239000012528 membrane Substances 0.000 title claims abstract description 99
- 239000000463 material Substances 0.000 title claims abstract description 70
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004098 Tetracycline Substances 0.000 claims abstract description 32
- 229960002180 tetracycline Drugs 0.000 claims abstract description 32
- 229930101283 tetracycline Natural products 0.000 claims abstract description 32
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 32
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 22
- 230000001788 irregular Effects 0.000 claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 19
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 18
- 239000004917 carbon fiber Substances 0.000 claims description 18
- 238000001523 electrospinning Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000004729 solvothermal method Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 35
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000877 morphologic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000243 solution Substances 0.000 description 16
- 238000002835 absorbance Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a bismuth molybdate/carbon flexible membrane photocatalytic
material, and a preparation method and application thereof. The microscopic morphology of the
bismuth molybdate/carbon flexible membrane photocatalytic material is the loading of irregular
bismuth molybdate nanoparticles and/or irregular bismuth molybdatenanorods on the surface of
carbon nanofibers. The diameter of the carbon nanofibers is 100 to 200 nm, the length of the
carbon nanofibers is 5 to 20 um, the diameter of the irregular bismuth molybdate nanoparticles
is 20 to 90 nm, the diameter of the irregular bismuth molybdatenanorods is 20 to 70 nm, and the
length of the irregular bismuth molybdatenanorods is 30 to 600 nm. The bismuth
molybdate/carbon flexible membrane provided by the present invention has better
photocatalytic activity and photocatalytic degradation performance, especially the degradation
rate regarding tetracycline can reach more than 97%. At the same time, the bismuth
molybdate/carbon flexible membrane has uniform morphological structure, good continuity,
green and pollution to free quality, and has flexibility, it is film to like as a whole
macroscopically, and is easier to be recovered and reused than powder materials, which can
effectively reduce costs and improve economic benefits.
Description
The invention relates to a bismuth molybdate/carbon flexible membrane photocatalytic material, and a preparation method and application thereof, and belongs to the technical field of inorganic photocatalytic materials.
In recent years, with the acceleration of the process of industrialization and the rapid development of social economy, people's demand for energy is increasing, and the resulting energy crisis and environmental pollution problems have become more and more serious. Among them, water body pollution in the environmental pollution problems seriously destroys the ecological balance and threatens the living environment and life and health of human beings. Therefore, the control and treatment of water body pollution has become one of the major problems that human society urgently needs to solve. Semiconductor photocatalystic technology is one of the effective methods to solve the problem of water body pollution due to its advantages of mild reaction conditions, stability and high efficiency, and no secondary pollutions, etc.
In 1972, Akira Fujishima and Kenichi Honda discovered that under light conditions, TiO 2 can be used to photodegrade water to produce oxygen and hydrogen. Therefore, TiO 2 has been extensively studied, and many photocatalysts based on TiO2 have been reported so far. However, TiO2 is a typical wide band gap semiconductor with a larger forbidden bandwidth and only responding to ultraviolet light, which only accounts for about 4% of the solar spectrum. Therefore, TiO2 has a very low utilization rate of sunlight. At the same time, the TiO 2 photocatalyst also has the disadvantages of low quantum efficiency and high photo-generated carrier recombination rate, etc., which limit its application. Therefore, it is very necessary to develop a narrow band gap semiconductor photocatalyst with visible light response.
Bi2MoO 6 is a typical Aurigillius phase-like perovskite semiconductor material with a forbidden bandwidth of about 2.70 eV, which can effectively utilize visible light in sunlight, and its advantages of excellent stability, low cost, and non-toxicity, etc., make it a research hotspot in the field of photocatalysis. Although Bi2MoO 6 has many advantages, it still has disadvantages of poor optical quantum efficiency and high photo-generated carrier recombination rate, etc., which limit its practical application. Therefore, the disadvantages thereof can be improved by modification methods. Common modification methods include Morphological Control (See: Sensors and Actuators B: Chemical, 2018, 277, 312 to 319), Ion Doping (See: Molecular Catalysis, 2017, 433, 301 to 312), Loading ofPrecious Metals (See: Materials Science in Semiconductor Processing, 2015, 34, 175 to 181), Semiconductor Compounding (See: Chemical Engineering Journal, 2021, 403, 126328), etc.
Chinese Patent Document CN105879855A discloses a preparation method of graphene-gamma-bismuth molybdatenanocomposite material, comprising the following steps of: 1) performing solvothermal reaction on graphene, bismuth nitrate and ethylene glycol together, and obtaining a graphene-ethylene glycol bismuth complex after filtration, washing and drying; and 2) uniformly dispersing the obtained complex in a sodium molybdate aqueous solution, adjusting the resulting solution system to pH value of 0 to 3, carrying out hydrothermal reaction, and obtaining the graphene-gamma-bismuth molybdatenanocomposite material after filtration, washing and drying. However, the graphene-gamma-bismuth molybdatenanocomposite material prepared by the patent is a powder, and the separation of powder materials in a solution is difficult, which is not conducive to the recycling of a Bi2MoO 6 photocatalyst.
SUMMARY Aiming at the shortcomings of the prior art, the present invention provides a bismuth molybdate/carbon flexible membrane photocatalytic material, and a preparation method and application thereof. The bismuth molybdate in the bismuth molybdate/carbon flexible membrane photocatalytic material provided by the present invention has both a low-temperature phase and a high-temperature phase, which can effectively separate photogenerated carriers. At the same time, carbon not only has strong adsorption, but also can accelerate the transmission rate of photogenerated electrons to further improve its photocatalytic performance.
TERMINOLOGY NOTE Spinning receiving distance: the distance from an electrospinning needle to a receiving device. Room temperature: it has a well-known meaning in the art, referring to 25 ±5 DEG C.
A bismuth molybdate/carbon flexible membrane photocatalytic material, wherein the microscopic morphology of the bismuth molybdate/carbon flexible membrane photocatalytic material is the loading of irregular bismuth molybdate nanoparticles and/or irregular bismuth molybdatenanorods on the surface of carbon nanofibers. Preferably according to the present invention, the diameter of the carbon nanofibers is 100 to 200 nm, the length of the carbon nanofibers is 5 to 20 um, the diameter of the irregular bismuth molybdate nanoparticles is 20 to 90 nm, the diameter of the irregular bismuth molybdatenanorods is 20 to 70 nm, and the length of the irregular bismuth molybdatenanorods is 30 to 600 nm.
According to the present invention, the preparation method of the bismuth molybdate/carbon flexible membrane photocatalytic material includes the following steps of:
(1)adding polyacrylonitrile to N,N-dimethylformamide and stirring evenly to obtain polyacrylonitrile sol, and performing electrospinning on the polyacrylonitrile sol to obtain a polyacrylonitrile fiber membrane;
(2)adding bismuth nitrate pentahydrate and a molybdenum source to the solvent and stirring evenly to obtain a mixed solution, then adding the polyacrylonitrile fiber membrane obtained in the step (1) into the mixed solution for solvothermal reaction; after the completion of the reaction, naturally cooling the mixed solution to room temperature, and obtaining a bismuth molybdate/carbon fiber membrane after washing and drying; and
(3)calcining the bismuth molybdate/carbon fiber membrane obtained in the step (2) in an air atmosphere to pre-oxidize the same, and then calcining and carbonizing in a nitrogen atmosphere to obtain the bismuth molybdate/carbon flexible membrane photocatalytic material.
Preferably according to the present invention, in the step (1), the weight-average molecular weight of the polyacrylonitrile is 150,000 to 250,000, and further preferably 150,000. Preferably according to the present invention, in the step (1), ratio of the mass of the polyacrylonitrile to the volume of N,N-dimethylformamide is (0.8 to 1.0): (8 to 10) in a unit of g/mL.
Preferably according to the present invention, in the step (1), the process conditions of the electrospinning are as follows: a temperature of 25 to 30 DEG C, a receiving distance of electrospinning of 15 to 20 cm, an ejection rate of 1.0 to 1.5 mL/h, a voltage of 15 to 25 kV, and a relative humidity of 15 to 30%.
Preferably according to the present invention, in the step (2), the molybdenum source is sodium molybdate or ammonium molybdate.
Preferably according to the present invention, in the step (2), the solvent is a mixed solution of ethylene glycol and absolute ethyl alcohol, wherein the volume ratio of ethylene glycol to absolute ethyl alcohol is 1: (1 to 2).
Preferably according to the present invention, in the step (2), the molar ratio of Bi" to Mo6 ' in the mixed solution is 2 : (0.8 to 1); and the concentration of bismuth nitrate pentahydrate in the mixed solution is 0.005 to 0.02 mmol/mL.
Preferably according to the present invention, in the step (2), the mass to volume ratio of the polyacrylonitrile fiber membrane to the mixed solution is (0.5 to 2): 1 in a unit of mg/mL.
Preferably according to the present invention, in the step (2), the temperature of the solvothermal reaction is 140 to 160 DEG C, and the reaction time is 20 to 24 h.
Preferably according to the present invention, in the step (2), the washing process is to wash the bismuth molybdate/carbon fiber membrane with each of deionized water and absolute ethyl alcohol successively for 3 to 5 times; and the drying process is to dry the washed product at 40 to 60 DEG C for 6 to 12 h.
Preferably according to the present invention, in the step (3), the calcination temperature of the pre-oxidation is 200 to 300 DEG C, the heating rate is 1 to 5 DEG C/min, and the holding time is 60 to 120 min; the calcination temperature of the carbonization is 600 to 900 DEG C, and the holding time is 60 to 120 min.
According to the present invention, an application of the bismuth molybdate/carbon flexible membrane photocatalytic material as described above for the photocatalytic degradation of tetracycline.
All chemicals used in the present invention are classified into analytical grade without further processing. TECHNICAL FEATURES AND BENEFICIAL EFFECTS OF THE PRESENT
1. In the present invention, the bismuth nitrate pentahydrate, molybdenum source and polyacrylonitrile fiber membrane are subjected to solvothermal reaction, and then the bismuth molybdate undergoes phase separation during the high-temperature calcination process to obtain a bismuth molybdate/carbon flexible membrane photocatalytic material structure that irregular bismuth molybdate nanoparticles and/or irregular bismuth molybdatenanorods are loaded on the surface of carbon nanofibers, which increases the specific surface area of the bismuth molybdate and render it to have better photocatalytic performance. At the same time, carbon not only has excellent adsorptivity, but also can accelerate the transfer rate of photogenerated electrons, thereby inhibiting the recombination of photogenerated electron-hole pairs, and further enhancing the photocatalytic activity and photocatalytic degradation performance of the bismuth molybdate/carbon flexible membrane photocatalytic material. Especially, the degradation rate regarding tetracycline can reach more than 97%.
2. The bismuth molybdate/carbon flexible membrane photocatalytic material prepared by the present invention uniform morphological structure, good continuity, green and pollution-free quality, and has flexibility, it is film-like as a whole macroscopically, and is easier to be recovered and reused than powder materials, which can effectively reduce costs and improve economic benefits.
3. The preparation method of the present invention is easy to operate, low in raw material cost, and suitable for large-scale industrial production, and is an economical and efficient preparation method for photocatalytic materials.
Fig. 1 is an X to ray diffraction spectrum of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1.
Fig. 2 is a scanning electron micrograph of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1;
wherein a is a low magnification scanning electron microscope (SEM) photograph; and b is a high magnification scanning electron microscope (SEM) photograph.
Fig. 3 is an optical photograph of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1.
Fig. 4 is an X-ray diffraction spectrum of the bismuth molybdate powder prepared in Comparative Example 1.
Fig. 5 is a scanning electron micrograph of the bismuth molybdate powder prepared in Comparative Example 1;
wherein a is a low magnification scanning electron microscope (SEM) photograph; and b is a high magnification scanning electron microscope (SEM) photograph.
Fig. 6 is an absorbance curve graph of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 under simulated sunlight through first dark reaction and then photocatalytic degradation of tetracycline.
Fig. 7 is an absorbance curve graph of the bismuth molybdate powder prepared in
Comparative Example 1 under simulated sunlight through first dark reaction and then photocatalytic degradation of tetracycline.
Fig. 8 is an absorbance curve graph of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 under simulated sunlight through direct photocatalytic degradation of tetracycline.
Fig. 9 is an absorbance curve graph of the bismuth molybdate powder prepared in Comparative Example 1 under simulated sunlight through direct photocatalytic degradation of tetracycline.
Fig. 10 is a comparison diagram of the degradation rate of tetracycline of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Examplel under simulated sunlight with or without dark reaction.
Fig. 11 is a comparison diagram of the degradation rate of tetracycline of the bismuth molybdate powder prepared in Comparative Example 1 under simulated sunlight with or without dark reaction.
Fig. 12 is a diagram of the degradation efficiency in four cycle experiments of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Examplel under simulated sunlight for direct photocatalytic degradation of tetracycline.
Fig. 13 is a diagram of the degradation efficiency in four cycle experiments of the bismuth molybdate powder prepared in Comparative Example 1 under simulated sunlight for direct photocatalytic degradation of tetracycline.
Hereinafter, the solution of the present invention will be further described below through specific Examples and drawings, which are not intended to limit the scope of the protection of the present invention.
The raw materials used in the Examples are all conventional raw materials, and the equipment used is all conventional equipment, all of which are commercially available.
The electrospinning device adopts a common electrospinning machine on the market; the propeller is a conventional plastic injector; and the average weight-average molecular weight of polyacrylonitrile (PAN) used in the Examples is 150,000.
Example 1
A preparation method of a bismuth molybdate/carbon (Bi2MoO 6 /C) flexible membrane photocatalytic material, including the following steps of:
(1)weighting 1 g of polyacrylonitrile (PAN) and adding into a beaker containing 9 mL of N,N-dimethylformamide (DMF) and stirring evenly to obtain polyacrylonitrile sol; then pouring the polyacrylonitrile sol into a plastic injector with a stainless needle, and electrospinning the same to a receiving plate, wherein the receiving distance between the stainless needle of the injector and the receiving plate is 15 cm, the advancing rate of the polyacrylonitrile sol is 1.0 mL/h, the voltage is 20kV, the electrospinning temperature is controlled at 25 DEG C, and the relative humidity is 20%, thereby obtaining a polyacrylonitrile fiber membrane;
(2)weighing 0.056 mmol of ammonium molybdate (molecular formula being (NH 4 ) 6Mo70 2 4 -4H2 0) and 0.8 mmol of bismuth nitrate pentahydrate, adding the same to a mixed solvent consisting of 20 mL of ethylene glycol and 40 mL of absolute ethyl alcohol and evenly stirring, pouring the resulting mixed solution into a reaction kettle, adding 100 mg of the polyacrylonitrile fiber membrane prepared in the step (1) for reaction at 160 DEG C for 24 h, then naturally cooling to room temperature, washing the fiber membrane using each of deionized water and absolute ethyl alcohol for 3 times, and then drying in a drying oven at 60 DEG C for 12 h after the washing to obtain a bismuth molybdate/carbon fiber membrane; and
(3)putting the bismuth molybdate/carbon fiber membrane obtained in the step (2) into a muffle furnace, raising the temperature to 250 DEG C at a heating rate of 1 DEG C/min, and holding for 120 min to pre-oxidize the same; putting the pre-oxidized bismuth molybdate/carbon fiber membrane into a tube furnace and introducing nitrogen, raising the temperature to 900 DEG C at a heating rate of 2 DEG C/min, and holding for 120 min to obtain the bismuth molybdate/carbon flexible membrane photocatalytic material.
The X-ray diffraction spectrum (XRD) of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in this Example is shown in Fig. 1. It can be known from Fig. 1 that low-temperature phase (JCPDS No. 21 to 0102) and high-temperature phase (JCPDS No. 22 to 0112) of Bi2MoO 6 appear in the bismuth molybdate/carbon flexible membrane photocatalytic material, and a weak carbon peak appears.
The scanning electron microscope (SEM) of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in this Example is shown in Fig. 2. It can be seen from Fig. 2 that Bi2MoO 6 nanoparticles and Bi2MoO 6 nanorods are loaded on the surface of carbon nanofibers, and the morphology is uniform and continuous; the diameter of bismuth molybdate nanoparticles is 20 to 90 nm, the diameter of bismuth molybdatenanorods is 20 to 70 nm, the length of bismuth molybdatenanorods is 30 to 600 nm, the diameter of carbon nanofibers is 100 to 200 nm, and the length of carbon nanofibers is 5 to 20 m.
The optical photograph of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in this Example is shown in Fig. 3. It can be seen from Fig. 3 that the bismuth molybdate/carbon flexible membrane has good flexibility.
Example 2 A preparation method of a bismuth molybdate/carbon flexible membrane photocatalytic material, including the following steps of:
(1)weighting 1 g of polyacrylonitrile (PAN) and adding into a beaker containing 9 mL of N,N-dimethylformamide (DMF) and stirring evenly to obtain polyacrylonitrile sol; then pouring the polyacrylonitrile sol into a plastic injector with a stainless needle, and electrospinning the same to a receiving plate, wherein the receiving distance between the stainless needle of the injector and the receiving plate is 15 cm, the advancing rate of the polyacrylonitrile sol is 1.0 mL/h, the voltage is 20kV, the electrospinning temperature is controlled at 25 DEG C, and the relative humidity is 20%, thereby obtaining a polyacrylonitrile fiber membrane; (2)weighing 0.4 mmol of sodium molybdate and 0.8 mmol of bismuth nitrate pentahydrate, adding the same to a mixed solvent consisting of 20 mL of ethylene glycol and 40 mL of absolute ethyl alcohol and evenly stirring, pouring the resulting mixed solution into a reaction kettle, adding 50 mg of the polyacrylonitrile fiber membrane prepared in the step (1) for reaction at 140 DEG C for 24 h, then naturally cooling to room temperature, washing the fiber membrane using each of deionized water and absolute ethyl alcohol for 3 times, and then drying in a drying oven at 60 DEG C for 12 h after the washing to obtain a bismuth molybdate/carbon fiber membrane; and
(3)putting the bismuth molybdate/carbon fiber membrane obtained in the step (2) into a muffle furnace, raising the temperature to 250 DEG C at a heating rate of 2 DEG C/min, and holding for 120 min to pre-oxidize the same; putting the pre-oxidized bismuth molybdate/carbon fiber membrane into a tube furnace and introducing nitrogen, raising the temperature to 900 DEG C at a heating rate of 2 DEG C/min, and holding for 120 min to obtain the bismuth molybdate/carbon flexible membrane photocatalytic material.
Example 3
A preparation method of a bismuth molybdate/carbon flexible membrane photocatalytic material, including the following steps of:
(1)weighting 1 g of polyacrylonitrile and adding into a beaker containing 10 mL of N,N-dimethylformamide and stirring evenly to obtain polyacrylonitrile sol; then pouring the polyacrylonitrile sol into a plastic injector with a stainless needle, and electrospinning the same to a receiving plate, wherein the receiving distance between the stainless needle of the injector and the receiving plate is 15 cm, the advancing rate of the polyacrylonitrile sol is 1.0 mL/h, the voltage is 20 kV, the electrospinning temperature is controlled at 25 DEG C, and the relative humidity is 20%, thereby obtaining a polyacrylonitrile fiber membrane;
(2)weighing 0.5 mmol of sodium molybdate and 1.0 mmol of bismuth nitrate pentahydrate, adding the same to a mixed solvent consisting of 20 mL of ethylene glycol and 40 mL of absolute ethyl alcohol and evenly stirring, pouring the resulting mixed solution into a reaction kettle, adding 50 mg of the polyacrylonitrile fiber membrane prepared in the step (1) for reaction at 160 DEG C for 24 h, then naturally cooling to room temperature, washing the fiber membrane using each of deionized water and absolute ethyl alcohol for 3 times, and then drying in a drying oven at 60 DEG C for 12 h after the washing to obtain a bismuth molybdate/carbon fiber membrane; and
(3)putting the bismuth molybdate/carbon fiber membrane obtained in the step (2) into a muffle furnace, raising the temperature to 300 DEG C at a heating rate of 1 DEG C/min, and holding for 120 min to pre-oxidize the same; putting the pre-oxidized bismuth molybdate/carbon fiber membrane into a tube furnace and introducing nitrogen, raising the temperature to 800 DEG C at a heating rate of 2 DEG C/min, and holding for 120 min to obtain the bismuth molybdate/carbon flexible membrane photocatalytic material.
Example 4
A preparation method of a bismuth molybdate/carbon flexible membrane photocatalytic material, including the following steps of:
(1)weighting 0.8 g of polyacrylonitrile and adding into a beaker containing 8 mL of N,N-dimethylformamide and stirring evenly to obtain polyacrylonitrile sol; then pouring the polyacrylonitrile sol into a plastic injector with a stainless needle, and electrospinning the same to a receiving plate, wherein the receiving distance between the stainless needle of the injector and the receiving plate is 15 cm, the advancing rate of the polyacrylonitrile sol is 1.0 mL/h, the voltage is 20 kV, the electrospinning temperature is controlled at 25 DEG C, and the relative humidity is 20%, thereby obtaining a polyacrylonitrile fiber membrane;
(2)weighing 0.042 mmol of ammonium molybdate and 0.6 mmol of bismuth nitrate pentahydrate, adding the same to a mixed solvent consisting of 20 mL of ethylene glycol and
40 mL of absolute ethyl alcohol and evenly stirring, pouring the resulting mixed solution into a reaction kettle, adding 50 mg of the polyacrylonitrile fiber membrane prepared in the step (1) for reaction at 140 DEG C for 20 h, then naturally cooling to room temperature, washing the fiber membrane using each of deionized water and absolute ethyl alcohol for 3 times, and then drying in a drying oven at 60 DEG C for 12 h after the washing to obtain a bismuth molybdate/carbon fiber membrane; and
(3)putting the bismuth molybdate/carbon fiber membrane obtained in the step (2) into a muffle furnace, raising the temperature to 250 DEG C at a heating rate of 1 DEG C/min, and holding for 120 min to pre-oxidize the same; putting the pre-oxidized bismuth molybdate/carbon fiber membrane into a tube furnace and introducing nitrogen, raising the temperature to 600 DEG C at a heating rate of1 DEG C/min, and holding for 60 min to obtain the bismuth molybdate/carbon flexible membrane photocatalytic material.
Comparative Example 1
A preparation method of a bismuth molybdate powder photocatalytic material, including the following steps of:
weighing 0.056 mmol of ammonium molybdate and 0.8 mmol of bismuth nitrate pentahydrate, adding the same to a mixed solvent consisting of 20 mL of ethylene glycol and 40 mL of absolute ethyl alcohol and evenly stirring, pouring the resulting mixed solution into a reaction kettle for reaction at 160 DEG C for 24 h, then naturally cooling to room temperature, washing the precipitate using each of deionized water and absolute ethyl alcohol for 3 times, and then drying the precipitate in a drying oven at 60 DEG C for 12 h after the washing to obtain a bismuth molybdate powder.
The X-ray diffraction spectrum (XRD) of the bismuth molybdate powder prepared in this comparative example is shown in Fig. 4. It can be known from Fig. 4 that the XRD of the bismuth molybdate powder corresponds well to the low- temperature phase of Bi2MoO 6
(JCPDS No. 21-0102), but there is no high-temperature phase (JCPDS No. 22-0112).
The scanning electron microscope (SEM) of the bismuth molybdate powder prepared in this comparative example is shown in Fig. 5. It can be seen from Fig. 5 that bismuth molybdate powder is a microsphere composed of nanosheets with a thickness of about 20 nm, and the diameter of the microsphere is about 1 m.
It can be known from Fig. 1 to 5 that compared with the micron-sized bismuth molybdate powder prepared in Comparative Example 1, the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1is a nano material, which has a nano effect that the bismuth molybdate powder does not possess. In addition, the phase separation of bismuth molybdate in the bismuth molybdate/carbon flexible membrane photocatalytic material, and the presence of a high-temperature phase and a low-temperature phase at the same time will have a better photocatalytic effect than bismuth molybdate powder with only a high-temperature phase. Moreover, the bismuth molybdate/carbon flexible membrane is easier to be recovered and reused than bismuth molybdate powder.
Application Example 1
First dark reaction and secondary photocatalytic degradation of tetracycline are carried out.
The bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 and the bismuth molybdate powder prepared in Comparative Example 1 are used in the photocatalytic degradation experiment of tetracycline, the simulated light source used is an 800 W xenon lamp and the concentration of a tetracycline solution is 20 mg/L, and the steps are as follows:
respectively dispersing 40 mg of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 and 40 mg of the bismuth molybdate powder prepared in Comparative Example 1 into 40 mL of 20 mg/L tetracycline solution, putting the same in a dark box for stirring and adsorbing for 30 min until reaching adsorption equilibrium; then turning on an xenon lamp of the simulated sunlight source to irradiate the solution, taking 4 mL of the solution every 10 min, centrifuging at 8000 rpm for 5 min in a centrifuge, taking a supernatant, using a UV-2550 spectrophotometer to measure the absorbance, the detection wavelength being 200 to 500 nm, and after the completion of the reaction, recovering the precipitate to complete the recovery of the catalyst.
Fig. 6 is an absorbance curve graph of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 under simulated sunlight for photocatalytic degradation of tetracycline, and Fig. 7 is an absorbance curve graph of the bismuth molybdate powder prepared in Comparative Example 1 under simulated sunlight for photocatalytic degradation of tetracycline.
It can be known from the Figs. 6 and 7 that the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 has better adsorption and photocatalytic degradation capabilities than the bismuth molybdate powder prepared in Comparative Example 1.
Application Example 2
Direct photocatalytic degradation of tetracycline without dark reaction
The bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 and the bismuth molybdate powder prepared in Comparative Example 1 are used in the photocatalytic degradation experiment of tetracycline, the simulated light source used is an 800 W xenon lamp and the concentration of a tetracycline solution is 20 mg/L, and the steps are as follows:
respectively dispersing 40 mg of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 and 40 mg of the bismuth molybdate powder prepared in Comparative Example 1 into 40 mL of 20 mg/L tetracycline solution, putting the solution in a dark box, turning on an xenon lamp of the simulated sunlight source to irradiate the solution, taking 4 mL of the solution every 10 min, centrifuging at 8000 rpm for 5 min in a centrifuge, taking a supernatant, using a UV-2550 spectrophotometer to measure the absorbance, the detection wavelength being 200 to 500 nm, and after the completion of the reaction, recovering the precipitate to complete the recovery of the catalyst.
Fig. 8 is an absorbance curve graph of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 under simulated sunlight for photocatalytic degradation of tetracycline, and Fig. 9 is an absorbance curve graph of the bismuth molybdate powder prepared in Comparative Example 1 under simulated sunlight for photocatalytic degradation of tetracycline.
Fig. 10 is a comparison diagram of the degradation rate of tetracycline of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in the Example 1 under simulated sunlight with or without dark reaction, and Fig. 11 is a comparison diagram of the degradation rate of tetracycline of the bismuth molybdate powder prepared in Comparative Example 1 under simulated sunlight with or without dark reaction.
It can be known from the Fig. 8 and 9 that the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 has better photocatalytic degradation capability than the bismuth molybdate powder prepared in Comparative Example 1.
It can be known from the Fig. 10 and11 that the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 has basically the same final degradation rate with or without dark reaction; the bismuth molybdate powder prepared in Comparative Example 1 also has basically the same final degradation rate with or without dark reaction, and the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 can better degrade tetracycline than the bismuth molybdate powder prepared in Comparative Example 1.
Application Example 3
Cyclic performance test of direct light degradation of tetracycline of the photocatalytic material prepared in Example 1 and Comparative Example 1.
The method of cyclic performance test includes the steps as follows:
respectively dispersing the bismuth molybdate/carbon flexible membrane photocatalytic material and bismuth molybdate powder recovered in Application Example 2 into 40 mL of 20 mg/L tetracycline solution, putting the same in a dark box, turning on an xenon lamp of the simulated sunlight source to irradiate the solution, taking 4 mL of the solution every 10 min, centrifuging at 8000 rpm for 5 min in a centrifuge, taking a supernatant, using a UV-2550 spectrophotometer to measure the absorbance, the detection wavelength being 200 to 500 nm, after the completion of the reaction, recovering the precipitate, and repeating the above procedures three times in such way.
The degradation efficiency diagram in four cycles of recycling of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 under simulated sunlight for tetracycline is shown in Fig. 12, and the degradation efficiency diagram in four cycles of recycling of the Bi2MoO6 powder prepared in Comparative Example 1 under simulated sunlight for tetracycline is shown in Fig. 13.
It can be seen from the Fig. 12 and 13 that thefirst degradation rate of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 is as high as 97%, and after four cycles of recycling, the degradation efficiency of the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 is still very high, being 95.6%; while the first degradation rate of the bismuth molybdate powder prepared in Comparative Example 1 is 63.9%, and after four cycles of recycling, the photocatalytic degradation rate of the bismuth molybdate powder prepared in Comparative Example 1 is 58.3%.
By comparison, it can be seen that the bismuth molybdate/carbon flexible membrane photocatalytic material prepared in Example 1 exhibits a more excellent photocatalytic degradation effect on tetracycline, and has good stability and can be reused repeatedly, thereby greatly reducing the production cost.
Claims (10)
- Claims: 1. A bismuth molybdate/carbon flexible membrane photocatalytic material, wherein the microscopic morphology of the bismuth molybdate/carbon flexible membrane photocatalytic material is the loading of irregular bismuth molybdate nanoparticles and/or irregular bismuth molybdatenanorods on the surface of carbon nanofibers.
- 2. The bismuth molybdate/carbon flexible membrane photocatalytic material according to claim 1, wherein the diameter of the carbon nanofibers is 100 to 200 nm, the length of the carbon nanofibers is 5 to 20 um, the diameter of the irregular bismuth molybdate nanoparticles is 20 to 90 nm, the diameter of the irregular bismuth molybdatenanorods is 20 to 70 nm, and the length of the irregular bismuth molybdatenanorods is 30 to 600 nm.
- 3. A preparation method of the bismuth molybdate/carbon flexible membrane photocatalytic material according to claim 1, comprising the following steps of:(1) addingpolyacrylonitrile to N,N-dimethylformamide and stirring evenly to obtain polyacrylonitrile sol, and performing electrospinning on the polyacrylonitrile sol to obtain a polyacrylonitrile fiber membrane;(2) adding bismuth nitrate pentahydrate and a molybdenum source to the solvent and stirring evenly to obtain a mixed solution, then adding the polyacrylonitrile fiber membrane obtained in the step (1) into the mixed solution for solvothermal reaction; after the completion of the reaction, naturally cooling the mixed solution to room temperature, and obtaining a bismuth molybdate/carbon fiber membrane after washing and drying; and(3) calcining the bismuth molybdate/carbon fiber membrane obtained in the step (2) in an air atmosphere to pre-oxidize the same, and then calcining and carbonizing in a nitrogen atmosphere to obtain the bismuth molybdate/carbon flexible membrane photocatalytic material.
- 4. The preparation method according to claim 3, wherein in the step (1), the weight-average molecular weight of the polyacrylonitrile is 150,000 to 250,000; and the ratio of the mass of the polyacrylonitrile to the volume of N,N-dimethylformamide is (0.8 to 1.0): (8 to 10) in unit of g/mL.
- 5. The preparation method according to claim 3, wherein in the step (1), the process conditions of the electrospinning are as follows: a temperature of 25 to 30 DEG C, a receiving distance of electrospinning of 15 to 20 cm, an ejection rate of 1.0 to 1.5 mL/h, a voltage of 15 to 25 kV, and a relative humidity of 15 to 30%.
- 6. The preparation method according to claim 3, wherein in the step (2), the molybdenum source is sodium molybdate or ammonium molybdate; and the solvent is a mixed solution of ethylene glycol and absolute ethyl alcohol, wherein the volume ratio of ethylene glycol and absolute ethyl alcohol is 1: (1 to 2).
- 7. The preparation method according to claim 3, wherein in the step (2), the molar ratio of Bi3 to Mo6 in the mixed solution is 2 : (0.8 to 1); and the concentration of bismuth nitrate pentahydrate in the mixed solution is 0.005 to 0.02 mmol/mL.
- 8. The preparation method according to claim 3, wherein in the step (2), the mass to volume ratio of the polyacrylonitrile fiber membrane and the mixed solution is (0.5 to 2): 1 in a unit of mg/mL; the temperature of the solvothermal reaction is 140 to 160 DEG C, and the reaction time is 20 to 24 h; the washing process is to wash the bismuth molybdate/carbon fiber membrane with each of deionized water and absolute ethyl alcohol successively for 3 to 5 times; and the drying process is to dry the washed product at 40 to 60 DEG C for 6 to 12 h.
- 9. The preparation method according to claim 3, wherein in the step (3), the calcination temperature of the pre-oxidation is 200 to 300 DEG C, the heating rate is 1 to 5 DEG C/min, and the holding time is 60 to 120 min; the calcination temperature of the carbonization is 600 to 900 DEG C, and the holding time is 60 to 120 min.
- 10. An application of the bismuth molybdate/carbon flexible membrane photocatalytic material according to any one of claims 1 to 2 for the photocatalytic degradation of tetracycline.
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| CN115779889B (en) * | 2022-11-10 | 2024-05-03 | 中国林业科学研究院林产化学工业研究所 | Lignin charcoal/bismuth molybdate composite photocatalyst and preparation method and application thereof |
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