CN114425371A - Method for inducing self-assembly of bismuth-based photocatalytic material by biosurfactant and application - Google Patents
Method for inducing self-assembly of bismuth-based photocatalytic material by biosurfactant and application Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 160
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000000463 material Substances 0.000 title claims abstract description 160
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000003876 biosurfactant Substances 0.000 title claims abstract description 11
- 238000001338 self-assembly Methods 0.000 title claims abstract description 10
- 230000001939 inductive effect Effects 0.000 title claims description 8
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims abstract description 40
- 229930182490 saponin Natural products 0.000 claims abstract description 40
- 150000007949 saponins Chemical class 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
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- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 150000001621 bismuth Chemical class 0.000 claims abstract description 10
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims abstract description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000004820 halides Chemical class 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 26
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- 238000001035 drying Methods 0.000 claims description 13
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- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 11
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 11
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 10
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229940088710 antibiotic agent Drugs 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 5
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- -1 halogen salt Chemical class 0.000 claims description 3
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- MKUXAQIIEYXACX-UHFFFAOYSA-N aciclovir Chemical compound N1C(N)=NC(=O)C2=C1N(COCCO)C=N2 MKUXAQIIEYXACX-UHFFFAOYSA-N 0.000 claims description 2
- 229960004150 aciclovir Drugs 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical group 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 2
- 229960001193 diclofenac sodium Drugs 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
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- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
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- 230000003197 catalytic effect Effects 0.000 description 14
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 150000003456 sulfonamides Chemical class 0.000 description 2
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- WALXYTCBNHJWER-UHFFFAOYSA-N 2,4,6-tribromopyridine Chemical compound BrC1=CC(Br)=NC(Br)=C1 WALXYTCBNHJWER-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- 239000004480 active ingredient Substances 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 150000003141 primary amines Chemical class 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a self-assembly method and application of a biosurfactant-induced bismuth-based photocatalytic material, wherein the method comprises the following steps of: dispersing the saponin powder in a bismuth-based precursor solution by ultrasonic, fully stirring and then carrying out hydrothermal reaction; solutes of the bismuth-based precursor solution are A salt and bismuth salt; the A salt comprises one of halide, tungstate, molybdate and metavanadate. The invention firstly proposes that the saponin powder is used as a biological surfactant to induce the self-assembly of the bismuth-based photocatalytic material, wherein active groups in the saponin powder are attached to the surface of the bismuth-based photocatalytic material, so that the bismuth-based photocatalytic material can be induced to be self-assembled into a unique flower ball structure, and can be used as an activator to reduce the interfacial force between the bismuth-based photocatalytic material and water, thereby increasing the surface adsorption sites of the bismuth-based photocatalytic material and synergistically enhancing the photocatalytic activity of the bismuth-based photocatalytic material.
Description
Technical Field
The invention relates to the technical field of functional nano materials. More particularly, relates to a method for inducing self-assembly of a bismuth-based photocatalytic material by a biosurfactant and application thereof.
Background
Hydrogen peroxide (H)2O2) The hydrogen energy-saving hydrogen energy generation device is always considered to be a promising clean energy source which can replace hydrogen energy and can be used for a plurality of fields such as single-chamber battery power generation and the like. In particular, H2O2As a carrier of energy, its own energy density and compressed H2Equivalent, but H2O2Has a ratio of H2A safer storage mode and a more convenient transportation mode. At the same time, H2O2The multifunctional cleaning oxidant is also a multifunctional cleaning oxidant, and is applied to various chemical industry and environmental management fields, including paper pulp manufacturing and bleaching, electronic industry, disinfection industry, water treatment industry and the like. At present, H is produced2O2The most common commercial process is the anthraquinone process. The anthraquinone process uses noble metal as catalyst to react H with H2And O2Direct conversion to H2O2However, the anthraquinone process is expensive, and the industrial process is complicated and generates a large amount of toxic by-products, thereby limiting its wide use. In addition, H is catalyzed with noble metal catalytic materials2And O2The process of (a) also presents potential explosion hazards and high energy consumption problems. Therefore, an efficient and inexpensive H is sought2O2The production process is of critical importance.
Photocatalytic production of H from semiconductor catalytic material2O2Is considered to be a very promising route. Theoretically, water and oxygen abundant on earth can produce H by semiconductor photocatalysis2O2The process is as follows: first, valence band hole (VB h) is generated+) Oxidizing water to produce O2Then conduction band electron (CB e)-) Promotion of O2Two-electron reduction of (2) to produce H2O2. Thus, H is produced by photocatalysis2O2Is a new candidate for artificial photosynthesis. However, these redox reactions all have a positive change in the Gibbs free energy and do not favor H in thermodynamic principles2O2Is generated. And, O2Is usually performed as a one-electron reductionLeading the reaction to occur, forming superoxide radical, thereby inhibiting O2Is reduced by two electrons to form H2O2. In addition, the catalytic material may be generating H2O2Thereafter, by disproportionation or VBh+Oxidation, decomposition of H at the semiconductor surface2O2Resulting in a decrease in yield. Therefore, the photocatalytic material which has low manufacturing cost, good photocatalytic performance and can be recycled is searched and developed to produce H2O2Still is one of the important directions in the field of photocatalytic research. For this purpose, the photocatalytic material chosen: firstly, the photocatalyst has strong photocatalytic capacity; to O2High selectivity and promotion of O2Reduction, inhibition of H2O2Decomposing; the stability is good; low dosage, high efficiency, environmental protection and no toxicity.
The bismuth-based catalyst material has [ Bi ]2O2]2+Layer structures are favored in the field of photocatalysis as separation channels. As a typical bismuth-based catalytic material, bismuth-based composite oxides have been intensively studied in the field of photocatalysis, such as water splitting, N2Fixation and degradation of organic contaminants, etc. Meanwhile, the interlayer area of the bismuth-based composite oxide is used as an active center of a photocatalytic reaction, so that excellent activity/stability is endowed to the material. In addition, the orbitals of Bi 6s and Bi 6p contribute to the bismuth-based complex
Valence Band (VB) and Conduction Band (CB) of the double oxide, which results in a reduction of the band gap of the catalytic material, extending the light harvesting range into the visible region. In fact, hybridization can also occur between Bi 6s and O2 p, so that the dispersity of VB is improved, the transfer efficiency of VB photogenerated holes is improved, and the recombination with photogenerated electrons is inhibited. In addition, the bismuth-based composite oxide photocatalytic material can be prepared by a simple and low-energy-consumption strategy, such as a rapid and simple wet chemical method. More interestingly, the CB and VB positions of the bismuth-based composite oxide photocatalytic material can be effectively adjusted to adapt to various photocatalytic oxidation-reduction reactions. To increase the photocatalytic production of H2O2Several strategies were adopted by researchers. For example, Su et al used a hole formed by adding HCOOH to the reaction solutionShuttle machine for transferring holes directly from the valence band of BiOCl to HCOO-Generating HCOO. HCOO. further with OH-The reaction is carried out to form OH. (see: Internal Electric Field Assisted photochemical Generation of Hydrogen Peroxide over BiOCl with HCOOH, ACS Sustainable Chemistry&Engineering,2018,6, 8704-. Sn introduced by Wei et al regulates the growth of BiOCl to form an ultrathin nanosheet with surface oxygen vacancies. The separation of the photo-generated charges is accelerated by inducing an electric field in an interface by carrying out surface modification on BiOCl and redistributing charges on the interface. The modification of Sn reduces the work function of Sn-BiOCl and simultaneously improves the conduction band and the valence band, thereby improving the photocatalytic reducibility and O2-Provides a new strategy for modifying BiOCl Materials (see: interface electronic and oxygen fuels synthetic cationic performance of bismuth oxide, Journal of flame Materials,2021,402,123470).
In conclusion, the photocatalytic performance of the modified bismuth-based composite oxide photocatalytic material has been widely studied. However, there is still a lack of research on inducing self-assembly of bismuth-based composite oxides using biosurfactants.
Disclosure of Invention
The first purpose of the invention is to provide a method for inducing self-assembly of bismuth-based photocatalytic materials by a biosurfactant.
The second purpose of the invention is to provide a bismuth-based photocatalytic material.
The third purpose of the invention is to provide the application of the bismuth-based photocatalytic material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, a method for inducing self-assembly of a bismuth-based photocatalytic material by a biosurfactant comprises the following steps:
dispersing the saponin powder in the bismuth-based precursor solution by ultrasonic, fully stirring, and carrying out hydrothermal reaction.
Solutes of the bismuth-based precursor solution are A salt and bismuth salt; the A salt comprises one of halide, tungstate, molybdate and metavanadate.
The preparation method of the invention is to add the saponin powder as the biosurfactant into the precursor solution of the bismuth-based photocatalytic material, and then induce the bismuth-based photocatalytic material to grow and cure along different crystal faces in the hydrothermal process, so as to obtain the bismuth-based photocatalytic material with lower surface energy. The invention firstly proposes that the saponin powder is used as a biosurfactant to induce the growth of the bismuth-based photocatalytic material. Wherein, non-covalent interactions such as hydrogen bond, van der waals force interaction and the like can be formed between the saponin powder and the catalytic material so as to induce the catalytic material to self-assemble into a unique structure. Meanwhile, active groups in the saponin powder are attached to the surface of the bismuth-based photocatalytic material, so that the interfacial force between the bismuth-based photocatalytic material and water can be reduced, the surface energy of the bismuth-based photocatalytic material is further reduced, the surface adsorption sites of the bismuth-based photocatalytic material are increased, and the photocatalytic activity of the bismuth-based photocatalytic material is synergistically enhanced.
Further, in the above method, the mass ratio of the total mass of the salt A and the bismuth salt (solute of the bismuth-based precursor solution) to the saponin powder is 1: 0.05-0.5.
The molar ratio of the A salt to the bismuth salt is 1: 1-2.
The solvent of the bismuth-based precursor solution is water and alcohol; preferably, the alcohol is ethanol or ethylene glycol. Wherein, the amount of the solvent and the solute in the bismuth-based precursor solution can be adjusted according to the need, for example, the mass volume ratio of the solute to the solvent is 1-5g:80-200 mL.
The volume ratio of the alcohol to the water is 1: 5-10.
According to a particular embodiment of the invention, the solvent is an aqueous ethanol solution.
The halogen salt is one of sodium chloride, potassium bromide and potassium iodide.
The bismuth salt is bismuth nitrate pentahydrate.
The tungstate is sodium tungstate.
The molybdate is sodium molybdate.
The metavanadate is ammonium metavanadate.
The dispersion mode of dispersing the saponin powder in the bismuth-based precursor solution is preferably ultrasonic dispersion, more preferably the time of ultrasonic treatment is 0.5-1h, wherein ultrasonic dispersion can more optimally and uniformly disperse the saponin powder in the bismuth-based precursor solution, and further more optimally regulate and control the structure of the bismuth-based photocatalytic material.
The stirring time is 0.5-1 hour. The saponin powder can be uniformly dispersed in the bismuth-based precursor solution within the time range.
The hydrothermal reaction is carried out for 16-24 hours at the temperature of 160-200 ℃. For example, the hydrothermal reaction is carried out at 160-180 ℃ for 18-20 hours, the hydrothermal reaction is carried out at 180-200 ℃ for 18-20 hours, and the like.
The method further comprises washing and drying after the hydrothermal reaction.
Preferably, the drying is under vacuum. Wherein, the vacuum drying is to prevent the bismuth-based photocatalytic material from agglomerating in the drying process.
More preferably, the drying is performed in a vacuum environment at a temperature of 70 to 105 ℃ for 6 to 8 hours.
The saponin powder is nano-scale and/or micro-scale saponin powder. For example, the particle size of the saponin powder is 1 nm to 1000 microns, 10 nm to 100 microns, 50nm to 100 microns, 100nm to 50 microns, or the like. Wherein, the nano-scale and/or micron-scale saponin powder can be more uniformly attached to the surface of the bismuth-based photocatalytic material, so that the structure of the bismuth-based photocatalytic material can be more optimally regulated and controlled.
In a second aspect, the invention provides a bismuth-based photocatalytic material prepared by the above preparation method.
In a third aspect, the invention provides a bismuth-based photocatalytic material for producing H under photocatalysis2O2Or in photocatalytic degradation of antibiotics.
Preferably, the antibiotic comprises one or more of sulfanilamide, diclofenac sodium, tetracycline, acyclovir.
Further, bismuth-based photocatalytic material is used for photocatalytic H production2O2The use ofThe method comprises the following steps:
and ultrasonically dispersing the bismuth-based photocatalytic material into deionized water for illumination.
Furthermore, the light source of the illumination is visible light with the wavelength being more than or equal to 420 nm.
According to the specific embodiment of the invention, the mass-to-volume ratio of the bismuth-based photocatalytic material to the deionized water is 10-50mg:50-200 mL.
According to the specific embodiment of the invention, the mass-to-volume ratio of the bismuth-based photocatalytic material to the deionized water is 10mg:50 mL.
According to the specific embodiment of the invention, the mass-to-volume ratio of the bismuth-based photocatalytic material to the deionized water is 20mg:50 mL.
According to the specific embodiment of the invention, the mass-to-volume ratio of the bismuth-based photocatalytic material to deionized water is 50mg:50 mL.
Further, the bismuth-based photocatalytic material is used for photocatalytic degradation of antibiotics, and the application comprises the following steps:
and ultrasonically dispersing the bismuth-based photocatalytic material into an aqueous solution of antibiotics for illumination.
Furthermore, the light source of the illumination is visible light with the wavelength being more than or equal to 420 nm.
According to a particular embodiment of the invention, the concentration of the aqueous solution of the antibiotic is between 1 and 10 ppm; the mass volume ratio of the bismuth-based photocatalytic material to the aqueous solution of the antibiotic is 10-50mg:50-200 mL.
According to a particular embodiment of the invention, the concentration of the aqueous solution of the antibiotic is 3 ppm.
According to a particular embodiment of the invention, the concentration of the aqueous solution of the antibiotic is 10 ppm.
The invention has the following beneficial effects:
1. the preparation method of the bismuth-based photocatalytic material mainly utilizes saponin powder as a biosurfactant to induce the bismuth-based precursor to be self-assembled into the bismuth-based photocatalytic material with a flower-ball-shaped structure. Active groups in the saponin powder are attached to the surface of the photocatalytic material, so that the self-assembly of the bismuth-based photocatalytic material can be induced, the active groups can be used as active ingredients to reduce the surface energy of the bismuth-based photocatalytic material, and the migration efficiency of carriers of the bismuth-based photocatalytic material is synergistically improved, so that the photocatalytic activity of the bismuth-based photocatalytic material is enhanced.
2. The bismuth-based photocatalytic material provided by the invention has stable structure and is respectively used for producing H through photocatalysis2O2And photocatalytic degradation of antibiotics, H2O2The yield can reach 100.3 mu mol/L, and the degradation rate of the sulfanilamide is about 1.2 to 12.8 times of that of the bismuth-based photocatalytic material prepared by the conventional method.
3. The preparation method of the bismuth-based photocatalytic material provided by the invention is simple in process, convenient to operate and suitable for large-scale production and application.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows a scanning electron microscope image of the bismuth-based photocatalytic material SA-BiOCl prepared in example 1;
FIG. 2 shows a transmission electron microscope image of the bismuth-based photocatalytic material SA-BiOCl prepared in example 1;
fig. 3 shows a scanning electron microscope image of the bismuth-based photocatalytic material SA-BiOBr prepared in example 9;
fig. 4 shows a transmission electron microscope image of the bismuth-based photocatalytic material SA-BiOBr prepared in example 9;
fig. 5 shows a scanning electron microscope image of the bismuth-based photocatalytic material SA-bini prepared in example 17;
fig. 6 shows a transmission electron microscope image of the bismuth-based photocatalytic material SA-bini prepared in example 17;
fig. 7 shows the fourier transform infrared spectra of the bismuth-based photocatalytic material obtained in example 1 and comparative example 1 and the saponin powder;
fig. 8 shows fourier transform infrared spectra of the bismuth-based photocatalytic materials obtained in example 9 and comparative example 2;
fig. 9 shows fourier transform infrared spectra of the bismuth-based photocatalytic materials obtained in example 17 and comparative example 3;
fig. 10 is a graph showing a comparison of fluorescence spectra of the bismuth-based photocatalytic materials obtained in example 1 and comparative example 1;
fig. 11 shows XRD comparison patterns of the bismuth-based photocatalytic materials prepared in example 1, example 9, example 17, and comparative examples 1 to 3;
fig. 12 shows a degradation contrast diagram of the bismuth-based photocatalytic material photocatalytic degradation sulfanilamide prepared in example 1 and comparative example 1;
fig. 13 shows a degradation contrast diagram of the bismuth-based photocatalytic material photocatalytic degradation sulfonamide prepared in example 9 and comparative example 2;
fig. 14 shows a degradation contrast diagram of the bismuth-based photocatalytic material photocatalytic degradation sulfonamide prepared in example 17 and comparative example 3;
FIG. 15 shows the photocatalytic H production of the bismuth-based photocatalytic materials obtained in example 1 and comparative example 12O2Yield comparison of (2).
Detailed Description
In order to further understand the technical features of the present invention, the present invention is described in detail with reference to the specific embodiments below. The embodiments are given by way of illustration only and not by way of limitation, and any insubstantial modifications, based on the present disclosure, may be made by those skilled in the art without departing from the scope of the present disclosure.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The reactants used in the following examples, bismuth (III) nitrate pentahydrate, sodium chloride, potassium bromide, potassium iodide, absolute ethanol, powdered saponin, methanol, formic acid, and hydrogen peroxide, were all commercially available analytical grade, and deionized water was prepared.
The following examples were SEM-tested using a SU-8000 scanning electron microscope of Hitachi, Japan, at an acceleration voltage of 100 kV;
the following examples were subjected to TEM test using a HT7700 transmission electron microscope of Hitachi, Japan, at an acceleration voltage of 100 kV;
the following examples were carried out using an infrared spectrometer of the Bruker VERTEX 700 type, Germany, for the analysis of the structure of functional groups, scanning over a wave number in the range 4000--1；
The following test examples were subjected to photocatalytic tests in a multi-position photochemical reactor under irradiation of 300W xenon lamp simulated sunlight (. lamda. gtoreq.420 nm). The concentration of sulfanilamide was determined using a high performance liquid chromatography system of LC-20AT Japan AT 275nm using a tunable ultraviolet absorption detector and a Roc-C18 column (150 mm. times.4.6 mm,5 μm).
Example 1
The preparation method of the bismuth-based photocatalytic material specifically comprises the following steps:
weighing 2mmol of Bi (NO)3)3·5H2O powder (0.97g) and 2mmol NaCl powder (0.117g) are dissolved in 10mL of absolute ethyl alcohol, 70mL of deionized water is added to obtain a bismuth-based precursor solution, and the saponin powder with the mass ratio of the bismuth-based precursor salt to the saponin powder being 0.1:1 is added and stirred vigorously for 30 min. The solution was transferred to a 150mL Teflon lined autoclave, heated at 160 ℃ for 18h and then cooled. Washing and centrifuging the mixture for three times by using ethanol and deionized water at room temperature, and drying the mixture for 8 hours in vacuum drying at 70 ℃ to obtain SA-BiOCl.
As can be seen from FIG. 1, the SA-BiOCl prepared in this example is a flower ball structure with a diameter of 300-500 nm.
As can be seen from FIG. 2, the SA-BiOCl prepared in this example is a structure stacked by nanosheets having a diameter of 80-100 nm.
Example 2
A bismuth-based photocatalytic material was prepared in the same manner as in example 1 except that the temperature of the hydrothermal reaction was adjusted to 180 ℃.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 3
A bismuth-based photocatalytic material was prepared in the same manner as in example 1, except that the temperature of the hydrothermal reaction was adjusted to 200 ℃.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 4
A bismuth-based photocatalytic material was prepared in the same manner as in example 1 except that the hydrothermal reaction time was adjusted to 16 hours.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 5
A bismuth-based photocatalytic material was prepared in the same manner as in example 1, except that the hydrothermal reaction time was adjusted to 24 hours.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 6
A bismuth-based photocatalytic material was prepared in the same manner as in example 1 except that the mass ratio of the bismuth-based precursor salt to the saponin powder was adjusted to 1: 0.05.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 7
A bismuth-based photocatalytic material was prepared in the same manner as in example 1, except that the mass ratio of the bismuth-based precursor salt to the saponin powder was adjusted to 1: 0.2.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 8
A bismuth-based photocatalytic material was prepared in the same manner as in example 1 except that the mass ratio of the bismuth-based precursor salt to the saponin powder was adjusted to 1: 0.5.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 9
The preparation method of the bismuth-based photocatalytic material specifically comprises the following steps:
weighing 2mmol of Bi (NO)3)3·5H2Dissolving O powder (0.97g) and 2mmol KBr powder (0.238g) in 10mL of anhydrous ethanol, adding 70mL of deionized water to obtain bismuth-based precursor solution, and adding bismuth-based precursorVigorously stirring the saponin powder with the mass ratio of the body salt to the salt of 0.1:1 for 30 min. The solution was transferred to a 150mL Teflon lined autoclave, heated at 160 ℃ for 18h and then cooled. Washing and centrifuging for three times by using ethanol and deionized water at room temperature, and drying for 8 hours in vacuum drying at 70 ℃ to obtain SA-BiOBr.
As can be seen from FIG. 3, the SA-BiOBr prepared in this example is a flower ball structure with a diameter of 800-1000 nm.
As can be seen from FIG. 4, the SA-BiOBr prepared in this example is a structure stacked by nanosheets having a diameter of 80-100 nm.
Example 10
A bismuth-based photocatalytic material was prepared in the same manner as in example 9 except that the temperature of the hydrothermal reaction was adjusted to 180 ℃.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 11
A bismuth-based photocatalytic material was prepared in the same manner as in example 9 except that the temperature of the hydrothermal reaction was adjusted to 200 ℃.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 12
A bismuth-based photocatalytic material was prepared in the same manner as in example 9 except that the hydrothermal reaction time was adjusted to 16 hours.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 13
A bismuth-based photocatalytic material was prepared in the same manner as in example 9, except that the hydrothermal reaction time was adjusted to 24 hours.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 14
A bismuth-based photocatalytic material was prepared in the same manner as in example 9 except that the mass ratio of the bismuth-based precursor salt to the saponin powder was adjusted to 1: 0.05.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 15
A bismuth-based photocatalytic material was prepared in the same manner as in example 9 except that the mass ratio of the bismuth-based precursor salt to the saponin powder was adjusted to 1: 0.2.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 16
A bismuth-based photocatalytic material was prepared in the same manner as in example 9 except that the mass ratio of the bismuth-based precursor salt to the saponin powder was adjusted to 1: 0.5.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 17
The preparation method of the bismuth-based photocatalytic material specifically comprises the following steps:
weighing 2mmol of Bi (NO)3)3·5H2Dissolving O powder (0.97g) and KI powder (2 mmol) (0.332g) in 10mL of absolute ethanol, adding 70mL of deionized water to obtain a bismuth-based precursor solution, adding saponin powder with the mass ratio of the bismuth-based precursor salt to the saponin powder being 0.05:1, and then violently stirring for 30 min. The solution was transferred to a 150mL Teflon lined autoclave, heated at 160 ℃ for 18h and then cooled. Washing and centrifuging for three times by using ethanol and deionized water at room temperature, and drying for 8 hours in vacuum drying at 70 ℃ to obtain the SA-BiOI.
As can be seen from FIG. 5, the SA-BiOI obtained in this example was a flower-ball-shaped structure having a diameter of 1.5 to 2 μm.
As can be seen from FIG. 6, the SA-BiOI prepared in this example is a structure stacked by nanosheets having a diameter of 150-200 nm.
Example 18
A bismuth-based photocatalytic material was prepared in the same manner as in example 17 except that the temperature of the hydrothermal reaction was adjusted to 180 ℃.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 19
A bismuth-based photocatalytic material was prepared in the same manner as in example 17 except that the temperature of the hydrothermal reaction was adjusted to 200 ℃.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 20
A bismuth-based photocatalytic material was prepared in the same manner as in example 17 except that the hydrothermal reaction time was adjusted to 16 hours.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 21
A bismuth-based photocatalytic material was prepared in the same manner as in example 17 except that the hydrothermal reaction time was adjusted to 24 hours.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 22
A bismuth-based photocatalytic material was prepared in the same manner as in example 17 except that the mass ratio of the bismuth-based precursor salt to the saponin powder was adjusted to 1: 0.1.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 23
A bismuth-based photocatalytic material was prepared in the same manner as in example 17 except that the mass ratio of the bismuth-based precursor salt to the saponin powder was adjusted to 1: 0.2.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Example 24
A bismuth-based photocatalytic material was prepared in the same manner as in example 17 except that the mass ratio of the bismuth-based precursor salt to the saponin powder was adjusted to 1: 0.5.
The bismuth-based photocatalytic material prepared by the embodiment has a flower spherical structure formed by stacking nanosheets.
Comparative example 1
The preparation method of the bismuth-based photocatalytic material specifically comprises the following steps:
weighing 2mmol of Bi (NO)3)3·5H2O powder (0.97g) and 2mmol of NaCl powder (0.117g) were dissolved in 10mL of anhydrous ethanol, 70mL of deionized water was added, and after stirring for 30min, the mixed solution was transferred to a 150mL polytetrafluoroethylene-lined autoclave, heated at 160 ℃ for 18h, and then cooled. Washing and centrifuging the mixture for three times by using ethanol and deionized water at room temperature, and drying the mixture for 6 hours at 70 ℃ in vacuum to obtain the nano flaky BiOCl.
Comparative example 2
The preparation method of the bismuth-based photocatalytic material comprises the following steps:
weighing 2mmol of Bi (NO)3)3·5H2O powder (0.97g) and 2mmol of KBr powder (0.238g) were dissolved in 10mL of anhydrous ethanol, 70mL of deionized water was added thereto, and after stirring for 30min, the mixed solution was transferred to a 150mL polytetrafluoroethylene-lined autoclave, heated at 160 ℃ for 18 hours, and then cooled. And washing and centrifuging for three times by using ethanol and deionized water at room temperature, and drying for 6h in vacuum at 70 ℃ to obtain the nano flaky BiOBr.
Comparative example 3
The preparation method of the bismuth-based photocatalytic material comprises the following steps:
weighing 2mmol of Bi (NO)3)3·5H2O powder (0.97g) and 2mmol KI powder (0.332g) were dissolved in 10mL of anhydrous ethanol, 70mL of deionized water was added thereto, and after stirring for 30min, the mixed solution was transferred to a 150mL polytetrafluoroethylene-lined autoclave, heated at 160 ℃ for 18h, and then cooled. And washing and centrifuging the mixture for three times by using ethanol and deionized water at room temperature, and drying the mixture for 6 hours in vacuum at 70 ℃ to obtain the nano flaky BiOI.
Some test analysis
(one) the infrared spectra of the photocatalytic material SA-BiOCl obtained in comparative example 1, the photocatalytic material BiOCl obtained in comparative example 1 and pure soap angle powder (as shown in FIG. 7).
The infrared spectra (shown in FIG. 8) of the photocatalytic material SA-BiOBr obtained in comparative example 9 and the photocatalytic material BiOBr obtained in comparative example 2 were obtained.
The infrared spectra of the photocatalytic material SA-BiOI obtained in comparative example 17 and that of the photocatalytic material BiOI obtained in comparative example 3 (see FIG. 9)
As can be seen from FIG. 7, the length of the groove is 3550--1The peak at (A) may be the-OH stretching frequency due to intramolecular hydrogen bonding, and may also be due to the N-H stretching vibration peak, in which there are two bands for the primary amine and one band for the secondary amine and the imine. At 1616cm-1Is a deformation vibration peak of N-H, and SA-BiOCl is 2922cm-1And 1384cm-1The peak at (A) is significantly stronger than BiOCl, indicating more NH3+The groups were attached to the surface of SA-BiOCl due to the alkaline substance in the saponin powder. At 1056cm-1The position is a ring oscillation peak caused by C-H deformation in the nitrogen-containing heterocyclic ring. At 527cm-1The peak at (A) is a Bi-O stretching vibration peak, confirming the presence of Bi-O bonds in SA-BiOCl and BiOCl materials. The groups and the hydroxyl groups of the nitrogen-containing compound belong to hydrophilic free radicals, and more hydrophilic free radicals exist on the surface of the SA-BiOCl material, which shows that the surface free energy of the SA-BiOCl is smaller and the hydrophilicity is stronger.
A comparison of FIGS. 7, 8 and 9 shows that the IR spectra of SA-BiOBr and SA-BiOI show similar changes, with hydrophilic-OH and-NH groups on the surface2The amount is increased thereby reducing the surface free energy of the catalytic material.
(II) the fluorescence spectra of the photocatalytic material SA-BiOCl obtained in comparative example 1 and the photocatalytic material BiOCl obtained in comparative example 1 (see FIG. 10).
As can be seen from fig. 10, the fluorescence signal of SA-BiOCl is significantly reduced compared to BiOCl, which indicates that the hole-electron recombination rate on the surface of SA-BiOCl is reduced, i.e., the preparation method of example 1 can significantly improve the photocatalytic activity of the bismuth-based catalytic material.
(III) XRD patterns (shown in FIG. 11) of the photocatalytic material SA-BiOCl obtained in comparative example 1, the photocatalytic material SA-BiOBr obtained in example 9, the photocatalytic material SA-BiOI obtained in example 17, the photocatalytic material BiOCl obtained in comparative example 1, the photocatalytic material BiOBr obtained in comparative example 2, and the photocatalytic material BiOI obtained in comparative example 3 were compared.
As can be seen from fig. 11, the positions of the characteristic peaks of SA-BiOCl, SA-BiOBr, and SA-BiOI were not changed with respect to the bulk photocatalytic material obtained in the comparative example, which indicates that the crystal structure of the material after induction with the saponin powder was not changed, i.e., the crystal structures of the bismuth-based catalytic materials were not changed by the preparation methods of example 1, example 9, and example 17.
Test example 1: the bismuth-based catalytic material is used for photocatalytic degradation of sulfanilamide.
Experimental groups: 1) adding 25mg of SA-BiOCl prepared in example 1 into 50mL of 5ppm sulfanilamide aqueous solution, carrying out ultrasonic treatment for 0.5h at 25 ℃, and then stirring for 0.5h to obtain a uniform mixed solution so as to achieve adsorption balance;
2) taking the concentration of the mixed solution as an initial concentration, performing photodegradation on the mixed solution for 2 hours by using visible light with the wavelength lambda of more than or equal to 420nm, taking a sample once every 0.3 hour, taking about 1.5ml of the sample, centrifuging the sample at the rotating speed of 3000 rpm for 15 minutes, taking the centrifuged supernatant into a brown liquid phase small bottle, and storing the brown liquid phase small bottle in a refrigerator at 4 ℃ for later use. And (3) detecting all samples by adopting high performance liquid chromatography, wherein the mobile phase is as follows: methanol/0.1% aqueous formic acid solution 60/40 (V/V); the flow rate is 1.0 mL/min; the column temperature is 40 ℃; the sample volume is 10 mu L; and an ultraviolet detector for detecting the wavelength of 270 nm. When the photodegradation time is 120min, the degradation rate reaches 51.1% (as shown in FIG. 12).
Control group: the same experiment was conducted except that SA-BiOCl was changed to BiOCl prepared in comparative example 1, and as a result, the degradation rate was 4.0% when the photodegradation time was 120min (as shown in FIG. 12).
Test example 2: the bismuth-based catalytic material is used for photocatalytic degradation of sulfanilamide.
Experimental groups: 1) adding 25mg of SA-BiOBr prepared in example 9 into 50mL of 5ppm sulfanilamide aqueous solution, carrying out ultrasonic treatment for 0.5h at 25 ℃, and then stirring for 0.5h to obtain a uniform mixed solution so as to achieve adsorption balance;
2) taking the concentration of the mixed solution as an initial concentration, performing photodegradation on the mixed solution for 2 hours by using visible light with the wavelength lambda of more than or equal to 420nm, taking a sample once every 0.3 hour, taking about 1.5ml of the sample, centrifuging the sample at the rotating speed of 3000 rpm for 15 minutes, taking the centrifuged supernatant into a brown liquid phase small bottle, and storing the brown liquid phase small bottle in a refrigerator at 4 ℃ for later use. And (3) detecting all samples by adopting high performance liquid chromatography, wherein the mobile phase is as follows: methanol/0.1% aqueous formic acid solution 60/40 (V/V); the flow rate is 1.0 mL/min; the column temperature is 40 ℃; the sample volume is 10 mu L; and an ultraviolet detector for detecting the wavelength of 270 nm. When the photodegradation time was 120min, the degradation rate reached 61.9% (as shown in FIG. 13).
Control group: the same experiment was conducted except that SA-BiOBr was changed to BiOBr prepared in comparative example 2, resulting in a degradation rate of 52.1% when the photodegradation time was 120min (as shown in FIG. 13).
Test example 3: the bismuth-based catalytic material is used for photocatalytic degradation of sulfanilamide.
Experimental groups: 1) adding 25mg of the SA-BiOI prepared in the example 17 into 50mL of 5ppm sulfanilamide aqueous solution, carrying out ultrasonic treatment for 0.5h at the temperature of 25 ℃, and then stirring for 0.5h to ensure that the solution is a uniform mixed solution so as to achieve adsorption balance;
2) taking the concentration of the mixed solution as an initial concentration, performing photodegradation on the mixed solution for 2 hours by using visible light with the wavelength lambda of more than or equal to 420nm, taking a sample once every 0.3 hour, taking about 1.5ml of the sample, centrifuging the sample at the rotating speed of 3000 rpm for 15 minutes, taking the centrifuged supernatant into a brown liquid phase small bottle, and storing the brown liquid phase small bottle in a refrigerator at 4 ℃ for later use. And (3) detecting all samples by adopting high performance liquid chromatography, wherein the mobile phase comprises the following components: methanol/0.1% aqueous formic acid solution 60/40 (V/V); the flow rate is 1.0 mL/min; the column temperature is 40 ℃; the sample volume is 10 mu L; and an ultraviolet detector for detecting the wavelength of 270 nm. When the photodegradation time is 120min, the degradation rate reaches 12.1% (as shown in FIG. 14).
Control group: the same experimental group was operated except that the SA-BiOI was changed to the BiOI obtained in comparative example 3, resulting in a degradation rate of 7.1% when the photodegradation time was 120min (as shown in FIG. 14).
Test example 4: bismuth-based catalytic material for photocatalytic production of H2O2
Experimental groups: 1) 50mg of SA-BiOCl from example 1 were added to 50In mL deionized water solution, firstly carrying out ultrasonic treatment for 0.5h at 25 ℃, and then stirring for 0.5h to ensure that the solution is in a uniform mixed solution to reach O2Carrying out adsorption balance;
2) taking the concentration of the mixed solution as an initial concentration, then illuminating the mixed solution for 1.5 hours by using visible light with the wavelength lambda of more than or equal to 420nm, taking a sample once every 0.5 hour, taking about 2mL of the sample, centrifuging the sample at the rotating speed of 3000 rpm for 15 minutes, taking the centrifuged supernatant into a centrifugal tube, and storing the supernatant in a refrigerator at 4 ℃ for later use. All the samples were developed by iodometry, the absorbance was measured at 350nm using an ultraviolet spectrophotometer, and the yield was calculated against the standard line, wherein the yield was 100.3. mu. mol/L when the light irradiation time was 60min (as shown in FIG. 15).
Control group: the same experiment was conducted except that SA-BiOCl was changed to BiOCl prepared in comparative example 1, and as a result, the yield was 15.0. mu. mol/L (as shown in FIG. 15) when the light-irradiation time was 60 min.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A method for inducing self-assembly of a bismuth-based photocatalytic material by a biosurfactant is characterized by comprising the following steps of:
dispersing the saponin powder in a bismuth-based precursor solution by ultrasonic, fully stirring and then carrying out hydrothermal reaction;
solutes of the bismuth-based precursor solution are A salt and bismuth salt; the A salt comprises one of halide, tungstate, molybdate and metavanadate.
2. The method according to claim 1, wherein the mass ratio of the total mass of the A salt and the bismuth salt to the saponin powder is 1: 0.05-0.5.
3. The method according to claim 1, wherein the molar ratio of the a salt to the bismuth salt is 1: 1-2;
preferably, the solvent of the bismuth-based precursor solution is water and alcohol; more preferably, the alcohol is ethanol or ethylene glycol;
preferably, the volume ratio of the alcohol to the water is 1: 5-10;
preferably, the halogen salt is one of sodium chloride, potassium bromide and potassium iodide;
preferably, the bismuth salt is bismuth nitrate pentahydrate;
preferably, the tungstate is sodium tungstate;
preferably, the molybdate is sodium molybdate;
preferably, the metavanadate is ammonium metavanadate.
4. The method according to claim 1, wherein the stirring time is 0.5 to 1 hour.
5. The method as claimed in claim 1, wherein the hydrothermal reaction is carried out at 160-200 ℃ for 16-24 hours.
6. The method according to claim 1, further comprising washing and drying after the hydrothermal reaction;
preferably, the drying is under vacuum conditions;
more preferably, the drying is performed in a vacuum environment at a temperature of 70 to 105 ℃ for 6 to 8 hours.
7. The method of claim 1, wherein the saponin powder is a nano-sized and/or micro-sized saponin powder.
8. A bismuth-based photocatalytic material obtainable by the method according to any one of claims 1 to 7.
9. The bismuth-based photocatalytic material of claim 8 for producing H under photocatalysis2O2Or in photocatalytic degradation of antibiotics; preferably, the antibiotic comprises one or more of sulfanilamide, diclofenac sodium, tetracycline, acyclovir.
10. Use according to claim 9, characterised in that a bismuth-based photocatalytic material is used for the photocatalytic production of H2O2The application comprises the following steps:
ultrasonically dispersing the bismuth-based photocatalytic material into deionized water, and illuminating;
preferably, the light source of the illumination is visible light with the wavelength being more than or equal to 420 nm;
preferably, the bismuth-based photocatalytic material is used for photocatalytic degradation of antibiotics, said application comprising the steps of:
dispersing the bismuth-based photocatalytic material into an aqueous solution of an antibiotic, and illuminating;
preferably, the light source of the illumination is visible light with the wavelength being more than or equal to 420 nm.
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