CN115445616A - Preparation method and application of silver-doped bismuth tungstate heterojunction photocatalyst - Google Patents
Preparation method and application of silver-doped bismuth tungstate heterojunction photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 62
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 36
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 36
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 42
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 15
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 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 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003115 biocidal effect Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000015556 catabolic process Effects 0.000 claims description 23
- 238000006731 degradation reaction Methods 0.000 claims description 23
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000010865 sewage Substances 0.000 claims description 9
- 229960003405 ciprofloxacin Drugs 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000002019 doping agent Substances 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 15
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 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 description 11
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 241001198704 Aurivillius Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- JDIBGQFKXXXXPN-UHFFFAOYSA-N bismuth(3+) Chemical compound [Bi+3] JDIBGQFKXXXXPN-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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Images
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/23—
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- B01J35/39—
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- B01J35/51—
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a preparation method and application of a silver-doped bismuth tungstate heterojunction photocatalyst, wherein the preparation method comprises the following steps of S1, obtaining sodium tungstate aqueous solution, and recording the sodium tungstate aqueous solution as A solution; mixing bismuth nitrate, silver nitrate and deionized water, then adding nitric acid under dark conditions, and uniformly mixing to obtain a solution B; s2, under the stirring condition, mixing the solution ADropwise adding the mixed solution into the solution B, uniformly mixing, transferring the mixed solution into a closed reaction kettle for hydrothermal reaction, and reacting for 6 to 8 hours at the temperature of between 160 and 190 ℃; and S3, washing and drying the product obtained by the treatment of the S2 to obtain the silver-doped bismuth tungstate heterojunction photocatalyst. In the photocatalyst prepared by the invention, ag is used as Bi 2 WO 6 Dopant in host lattice structure and Bi supported in form of nanoparticles 2 WO 6 On the surface, the catalyst has large specific surface area and strong surface plasmon resonance, has good photocatalytic performance for the treatment of antibiotic wastewater, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of photochemical materials, in particular to a preparation method and application of a silver-doped bismuth tungstate heterojunction photocatalyst.
Background
The photocatalytic oxidation technology is a new environmental protection technology developed gradually from the 20 th century, and is excited by light to generate electron-hole pairs, so that active substances with strong oxidizability are generated and used for treating refractory substances in sewage. In addition, the photocatalyst has the advantages of no toxicity, no harm, no corrosiveness, reusability and the like, has the advantages of being incomparable with the traditional high-temperature and conventional catalytic technologies, and enables the photocatalytic oxidation technology to become a green environmental management technology with wide application prospect.
In recent years, visible light driven semiconductor photocatalysts have received much attention. Wherein, bi 2 WO 6 Has excellent stability and high-efficiency electron transmission capability, can be excited under the action of visible light and ultraviolet rays, and is a green catalytic material. Bi 2 WO 6 Belongs to an orthorhombic system and is Aurivillius type oxide with the simplest structure; it has a typical perovskite layer structure, and Bi is alternately formed along the c axis 2 O 2 Layer and WO 6 And (3) a layer. Bi 2 WO 6 The unique layered structure enables the photocatalyst to effectively degrade organic pollutants such as antibiotics and the like, and is considered as the photocatalyst with the most potential in antibiotic sewage treatment.
However, bi 2 WO 6 Has a large spectral width (2.8 eV), can only absorb light less than 450nm, and has the problems that photogenerated electrons and holes are easy to recombine, the separation efficiency of photogenerated carriers is low, and Bi is caused by the problems 2 WO 6 Has low photocatalytic activity, thereby limiting Bi 2 WO 6 The application in antibiotic sewage treatment.
Disclosure of Invention
The purpose of the invention is to increase Bi 2 WO 6 The specific surface area and reaction active sites are increased, so that the photocatalytic activity of the photocatalyst is improved, and the preparation method and the application of the silver-doped bismuth tungstate heterojunction photocatalyst are provided.
The inventors thought that Bi may be added to improve the photocatalytic activity 2 WO 6 Coupling with another semiconductor to form a heterostructure nanomaterial, or in Bi 2 WO 6 The nanoparticles are doped with metallic or non-metallic elements, and semiconductors modified by silver have promise in enhancing photocatalytic activity. Based on the research in this aspect, the invention uses Bi 2 WO 6 Is compounded with silver nano particles to increase Bi 2 WO 6 Photocatalytic activity of (1).
In the process of preparing the photocatalyst by the hydrothermal synthesis method, firstly, silver nitrate and bismuth nitrate are mixed and then sodium tungstate is added to prepare the photocatalyst; in the composite photocatalyst, ag is used as Bi 2 WO 6 Dopants in the host lattice structure, also loaded as nanoparticles in Bi 2 WO 6 The surface of the main crystal lattice ensures that the prepared photocatalyst has a 3D flower-shaped microsphere structure, and increases Bi 2 WO 6 The specific surface area and the reactive site of the bismuth (III) to further improve Bi 2 WO 6 The photocatalytic activity is realized, the effective separation of electron-hole pairs and the remarkable enhancement of visible light absorption are realized, and the finally obtained photocatalyst has good photocatalytic degradation performance on antibiotics.
In the preparation process, the silver nitrate is easy to decompose when exposed to light, and can be used after being prepared, and the silver nitrate is mixed with the bismuth nitrate and then stirred under a dark condition, otherwise, the photocatalytic efficiency of the material is influenced. The temperature of the hydrothermal reaction is 160-190 ℃, the reaction time is 6-8 h, preferably 7h, and the photocatalytic effect of the obtained material is optimal.
In order to sufficiently dissolve bismuth nitrate, nitric acid, preferably 1mol/L nitric acid, is added in an amount of 15mL (based on 5mmol of bismuth nitrate pentahydrate) in the dark in S1 of the present invention.
The specific scheme is as follows:
a preparation method of a silver-doped bismuth tungstate heterojunction photocatalyst comprises the following steps:
s1, obtaining a sodium tungstate aqueous solution, and recording the sodium tungstate aqueous solution as an A solution; mixing bismuth nitrate, silver nitrate and deionized water, then adding nitric acid under dark conditions, and uniformly mixing to obtain a solution B;
s2, dropwise adding the solution A into the solution B under the stirring condition, uniformly mixing, transferring the mixture into a closed reaction kettle for hydrothermal reaction, and reacting at 160-190 ℃ for 6-8 h;
and S3, washing and drying the product obtained by the treatment of the S2 to obtain the silver-doped bismuth tungstate heterojunction photocatalyst.
Further, in the S1, the concentration of the sodium tungstate aqueous solution is 0.1-0.5mmol/mL; in the solution B, the concentration of silver nitrate is 0.5-3mmol/L;
preferably, in the S1, the concentration of the nitric acid is 0.1-3mol/L, preferably 1-2mol/L, and the addition amount of the nitric acid is as follows: the addition of bismuth nitrate =5-40mL:3-12mmol, more preferably 10-20mL:3-12mmol.
Further, in the S2, the hydrothermal reaction is carried out for 7 hours at 180 ℃.
Further, in the step S3, the washed product is dried in vacuum at 75-85 ℃ for 23-26 h.
The invention also provides the silver-doped bismuth tungstate heterojunction photocatalyst prepared by the preparation method of the silver-doped bismuth tungstate heterojunction photocatalyst, wherein the silver-doped bismuth tungstate heterojunction photocatalyst is of a 3D flower-shaped microsphere structure, and the 3D flower-shaped microsphere structure is formed by overlapping nano sheets in a staggered mode.
Furthermore, the average diameter of the silver-doped bismuth tungstate heterojunction photocatalyst is 2-3 mu m, and the thickness of the silver-doped bismuth tungstate heterojunction photocatalyst is 45-55 nm.
Further, the XRD spectrum of the silver-doped bismuth tungstate heterojunction photocatalyst shows that Bi is contained 2 WO 6 Characteristic peak, no impurity peak, and peak intensity at 28.3 DEG and 32.9 DEG relative to orthorhombic Bi 2 WO 6 Changes in the standard cards indicate Ag + Into Bi 2 WO 6 In the lattice space of or in place of Bi 3+ Cause Bi 2 WO 6 Causing lattice distortion.
Furthermore, the molar concentration of Ag in the silver-doped bismuth tungstate heterojunction photocatalyst is 0.55-0.85%.
The invention also protects the application of the silver-doped bismuth tungstate heterojunction photocatalyst in degrading antibiotic-containing sewage.
Further, 40-50mg of the silver-doped bismuth tungstate heterojunction photocatalyst is added into the ciprofloxacin-containing sewage, the concentration of the ciprofloxacin is 1-10mg/L, and the degradation rate of the ciprofloxacin is 60-90% when the sewage is illuminated for 180 min.
Has the advantages that:
(1) In Bi 2 WO 6 During the synthesis process, firstly, silver nitrate is mixed with bismuth nitrate, ag is used as a doping agent, and nano-particle pair Bi 2 WO 6 Can increase Bi compared with the conventional silver doping method by modifying the inside and the surface of the material 2 WO 6 And enhances Bi 2 WO 6 The surface plasma resonance of (3) accelerates the migration rate of photon-generated carriers, thereby promoting Bi 2 WO 6 The photocatalytic performance of the material;
(2) In the preparation method provided by the invention, the used reagents are safe, the preparation conditions are mild, and good modification effect can be realized only by doping and modifying a small amount of silver, so that the preparation method has a good application prospect.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is one of SEM pictures of a photocatalyst provided in example 1 of the present invention;
FIG. 2 is a second SEM picture of the photocatalyst provided by the embodiment 1 of the present invention;
FIG. 3 is an XRD pattern of a photocatalyst provided by the present invention;
FIG. 4 is a graph showing the results of ciprofloxacin degradation experiments with photocatalysts according to the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1 silver-doped bismuth tungstate heterojunction photocatalyst and preparation method thereof
The preparation method of the photocatalyst by a hydrothermal synthesis method specifically comprises the following steps:
s1, weighing 2.5mmol of sodium tungstate dihydrate, dissolving the sodium tungstate dihydrate in 15mL of ultrapure water, and stirring until the sodium tungstate dihydrate is completely dissolved to prepare a solution A;
s2, weighing 5mmol of pentahydrate bismuth nitrate, adding 1mmol/L silver nitrate solution, and performing ultrasonic treatment by using an ultrasonic cleaner to accelerate dissolution so as to uniformly disperse the pentahydrate bismuth nitrate;
s3, under the dark condition, adding 15mL of 1mol/L nitric acid into the liquid of the S2, and stirring and mixing uniformly to obtain a solution B;
s4, slowly dripping the solution A into the solution B under the stirring condition, fully and uniformly mixing, transferring to a reaction kettle with a polytetrafluoroethylene lining, and reacting for 7 hours at 180 ℃;
and S5, respectively carrying out centrifugal washing on the reaction product in the S4 by using deionized water and absolute ethyl alcohol for 4-5 times, then placing the reaction product in a vacuum drying oven at 80 ℃, carrying out vacuum drying for 24 hours, and finally fully grinding the reaction product by using an agate mortar to prepare the photocatalyst.
In the preparation process, ag/Bi with Ag doping amounts of 0, 0.55%, 0.65%, 0.75%, 0.85% and 0.95% (n/n) are respectively obtained according to different addition amounts of silver nitrate 2 WO 6 A composite catalytic material.
Example 2
Morphology analysis of the photocatalyst prepared in example 1 was performed, and samples of the photocatalyst doped with 0.75% (n/n) Ag were selected, and SEM images at different magnifications are shown in FIGS. 1 and 2, and it can be seen that Ag/Bi 2 WO 6 The crystal is in a 3D flower-shaped microsphere structure, the grain sizes are basically consistent, and the flower-shaped microspheres Ag/Bi 2 WO 6 The particle diameter of the nanometer material is about 2 μm-3 μm, the thickness is about 50nm, and the size is irregular.
As is clear from FIGS. 1 and 2, the cubic structure of the complex is formed by the high density of 2D nano-flakes stacked alternately, and the nano-particles are polymerized alternately to form a hollow, uniformly sized flower-shaped microsphere structure with a large specific surface area and reactive sites, which may be 0.75% Ag/Bi 2 WO 6 The material has higher photocatalytic performance.
The morphology of the catalyst samples with other Ag doping amounts is similar to that of the silver doping sample with 0.75% (n/n).
Example 3
XRD analysis was performed on the sample prepared in example 1, and as shown in FIG. 3, from FIG. 3, the sample had four significant characteristic peaks, indicating four crystal planes each, and Bi appeared at about 28.3 °, 32.9 °, 47.2 °, 56.0 °, 58.7 °, 69.2 °, 76.3 ° and 78.4 ° in 2 θ 2 WO 6 Characteristic peaks respectively corresponding to orthorhombic systems Bi 2 WO 6 Crystal planes (131), (200), (202), (331), (262), (400), (103) and (204). These diffraction peaks and orthorhombic system Bi 2 WO 6 Standard card (C)PDF No. 39-0256), the results are completely consistent, and no impurity peak exists, which indicates that the purity of the sample is high. The intensity of diffraction peak of samples with different doping amounts is different, because the doping of ions has certain influence on the crystallinity of the samples.
Example 4
The sample prepared in example 1 was subjected to degradation test, and a 10mg/L ciprofloxacin aqueous solution was selected, and 40mg of the prepared sample was added, and the treatment effect was as shown in FIG. 4 with the lapse of treatment time. The Blank group was Blank and no catalyst was added.
As can be seen from fig. 4, CIP was not substantially degraded in the blank control without sample. Adding samples with different doping amounts, dark reacting for 30min, and then carrying out Ag/Bi 2 WO 6 The highest CIP adsorption rate can reach 37 percent and is higher than pure Bi 2 WO 6 25% of the total. In the photocatalytic reaction stage, ag/Bi with different doping amounts is added along with the increase of illumination time 2 WO 6 The degradation rates of the compounds are all in a descending trend; the CIP degradation rate is poor and is only about 50% under the condition of not doping Ag; while an excessively high doping amount, e.g., 0.85% Ag/Bi 2 WO 6 And 0.95% of Ag/Bi 2 WO 6 The degradation effect of (2) is relatively poor, and the degradation rate after illumination for 180min is about 60%. In addition, the composite materials with the other three horizontal doping amounts show better degradation performance. Wherein, when the Ag doping amount is 0.75%, the sample has the best photocatalysis effect, and the degradation rate is up to 87% after 180min of illumination.
Comparative example 1
Referring to example 1, a photocatalyst was prepared by a hydrothermal synthesis method, specifically including the steps of:
s1, weighing 2.5mmol of sodium tungstate dihydrate, dissolving the sodium tungstate dihydrate in 15mL of ultrapure water, and stirring until the sodium tungstate is completely dissolved to prepare a solution A;
s2, weighing 5mmol of bismuth nitrate pentahydrate, adding 1mmol/L of silver nitrate solution, and performing ultrasonic treatment by using an ultrasonic cleaner to accelerate dissolution so as to uniformly disperse the bismuth nitrate pentahydrate;
s3, adding 15mL of 1mol/L nitric acid into the liquid of the S2 at room temperature in a transparent glass container, and directly stirring and uniformly mixing to obtain a solution B without shading treatment;
s4, slowly dripping the solution A into the solution B under the stirring condition, fully and uniformly mixing, transferring to a reaction kettle with a polytetrafluoroethylene lining, and reacting for 7 hours at 180 ℃;
and S5, respectively carrying out centrifugal washing on the reaction product in the S4 for 4-5 times by using deionized water and absolute ethyl alcohol, then placing the reaction product in a vacuum drying oven at 80 ℃, carrying out vacuum drying for 24 hours, and finally fully grinding the reaction product by using an agate mortar to prepare the photocatalyst, wherein the doping amount of Ag is 0.75% (n/n).
The same degradation test was performed with reference to example 4, and the degradation rate was 53.2% after the sample was irradiated for 180 min.
Comparative example 2
Referring to example 1, a photocatalyst was prepared by a hydrothermal synthesis method, specifically including the steps of:
s1, weighing 2.5mmol of sodium tungstate dihydrate, dissolving the sodium tungstate dihydrate in 15mL of ultrapure water, and stirring until the sodium tungstate is completely dissolved to prepare a solution A;
s2, weighing 5mmol of pentahydrate bismuth nitrate, adding 1mmol/L silver nitrate solution, and performing ultrasonic treatment by using an ultrasonic cleaner to accelerate dissolution so as to uniformly disperse the pentahydrate bismuth nitrate;
s3, under the dark condition, adding 15mL of 1mol/L nitric acid into the liquid of the S2, and stirring and mixing uniformly to obtain a solution B;
s4, slowly dripping the solution A into the solution B under the stirring condition, transferring the solution A into a polytetrafluoroethylene-lined reaction kettle after fully and uniformly mixing, reacting for different times at 180 ℃, and taking six groups of 4h, 6h, 7h, 8h, 10h and 12h for carrying out comparison experiments;
and S5, respectively carrying out centrifugal washing on the reaction product in the S4 for 4-5 times by using deionized water and absolute ethyl alcohol, then placing the reaction product in a vacuum drying oven at 80 ℃, carrying out vacuum drying for 24 hours, and finally fully grinding the reaction product by using an agate mortar to prepare the photocatalyst, wherein the doping amount of Ag is 0.75% (n/n).
The same degradation test is carried out according to example 4, and the hydrothermal reaction time influences the appearance and performance of bismuth tungstate, and the excessively long and short hydrothermal reaction time can cause Ag/Bi 2 WO 6 The degradation effect is poor. Specifically, CIP degradation rates of samples corresponding to hydrothermal reactions of 4h, 6h, 7h, 8h, 10h and 12h after 180min of illumination are respectively 56.29%, 74.19%, 88.06%, 81.37%, 67.84%, 74.44% and 53.28%. It can be seen that Ag/Bi at different hydrothermal reaction times 2 WO 6 The CIP degradation rates of the catalysts varied widely with a maximum and minimum difference of 34.38%.
Comparative example 3
Referring to example 1, a photocatalyst was prepared by a hydrothermal synthesis method, specifically including the steps of:
s1, weighing 2.5mmol of sodium tungstate dihydrate, dissolving the sodium tungstate dihydrate in 15mL of ultrapure water, and stirring until the sodium tungstate is completely dissolved to prepare a solution A;
s2, weighing 5mmol of pentahydrate bismuth nitrate, adding 1mmol/L silver nitrate solution, and performing ultrasonic treatment by using an ultrasonic cleaner to accelerate dissolution so as to uniformly disperse the pentahydrate bismuth nitrate;
s3, under the dark condition, adding 40mL of 1mol/L nitric acid into the liquid of the S2, and stirring and mixing uniformly to obtain a solution B;
s4, slowly dripping the solution A into the solution B under the stirring condition, fully and uniformly mixing, transferring to a reaction kettle with a polytetrafluoroethylene lining, and reacting for 7 hours at 180 ℃;
and S5, respectively carrying out centrifugal washing on the reaction product in the S4 by using deionized water and absolute ethyl alcohol for 4-5 times, then placing the reaction product in a vacuum drying oven at 80 ℃, carrying out vacuum drying for 24 hours, and finally fully grinding the reaction product by using an agate mortar to prepare the photocatalyst, wherein the doping amount of Ag is 0.75% (n/n).
The same degradation test was performed with reference to example 4, and the degradation rate was 64.05% after the sample was irradiated for 180 min. It can be seen that too much addition of nitric acid results in too high acidity and poor degradation effect of the product generated by the reaction.
Comparative example 4
Referring to example 1, a photocatalyst was prepared by a hydrothermal synthesis method, specifically including the steps of:
s1, weighing 2.5mmol of sodium tungstate dihydrate, dissolving the sodium tungstate dihydrate in 15mL of ultrapure water, and stirring until the sodium tungstate is completely dissolved to prepare a solution A;
s2, weighing 5mmol of pentahydrate bismuth nitrate, adding 1mmol/L silver nitrate solution, and performing ultrasonic treatment by using an ultrasonic cleaner to accelerate dissolution so as to uniformly disperse the pentahydrate bismuth nitrate;
s3, under the dark condition, adding 5mL of 1mol/L nitric acid into the liquid of the S2, and stirring and mixing uniformly to obtain a solution B;
s4, slowly dripping the solution A into the solution B under the stirring condition, fully and uniformly mixing, transferring to a reaction kettle with a polytetrafluoroethylene lining, and reacting for 7 hours at 180 ℃;
and S5, respectively carrying out centrifugal washing on the reaction product in the S4 for 4-5 times by using deionized water and absolute ethyl alcohol, then placing the reaction product in a vacuum drying oven at 80 ℃, carrying out vacuum drying for 24 hours, and finally fully grinding the reaction product by using an agate mortar to prepare the photocatalyst, wherein the doping amount of Ag is 0.75% (n/n).
The same degradation test was performed with reference to example 4, and the degradation rate was 55.89% after the sample was irradiated for 180 min. Therefore, the adding amount of the nitric acid is too small, the bismuth nitrate is not completely dissolved, the reaction is insufficient, and the degradation effect of the generated product is poor.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of a silver-doped bismuth tungstate heterojunction photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, obtaining a sodium tungstate aqueous solution, and marking as an A solution; mixing bismuth nitrate, silver nitrate and deionized water, then adding nitric acid under dark conditions, and uniformly mixing to obtain a solution B;
s2, under the condition of stirring, dropwise adding the solution A into the solution B, uniformly mixing, transferring to a closed reaction kettle for hydrothermal reaction, and reacting for 6-8 h at 160-190 ℃;
and S3, washing and drying the product obtained by the treatment of the S2 to obtain the silver-doped bismuth tungstate heterojunction photocatalyst.
2. The preparation method of the silver-doped bismuth tungstate heterojunction photocatalyst as claimed in claim 1, wherein the preparation method comprises the following steps: in the S1, the concentration of the sodium tungstate aqueous solution is 0.1-0.5mmol/mL; in the solution B, the concentration of silver nitrate is 0.5-3mmol/L;
preferably, in the S1, the concentration of the nitric acid is 0.1-3mol/L, preferably 1-2mol/L, and the addition amount of the nitric acid is as follows: the addition of bismuth nitrate =5-40mL:3-12mmol.
3. The preparation method of the silver-doped bismuth tungstate heterojunction photocatalyst as claimed in claim 1, wherein the preparation method comprises the following steps: in the S2, the hydrothermal reaction is carried out for 7h at 180 ℃.
4. The preparation method of the silver-doped bismuth tungstate heterojunction photocatalyst as claimed in claim 1, wherein the preparation method comprises the following steps: and in the S3, the drying condition is that the washed product is dried in vacuum for 23-26 h at the temperature of 75-85 ℃.
5. The silver-doped bismuth tungstate heterojunction photocatalyst prepared by the preparation method of the silver-doped bismuth tungstate photocatalyst as claimed in any one of claims 1 to 4, is characterized in that: the silver-doped bismuth tungstate heterojunction photocatalyst is of a 3D flower-shaped microsphere structure, and the 3D flower-shaped microsphere structure is formed by overlapping nanosheets in a staggered mode.
6. The silver-doped bismuth tungstate heterojunction photocatalyst as claimed in claim 5, wherein: the average diameter of the silver-doped bismuth tungstate heterojunction photocatalyst is 2-3 mu m, and the thickness of the silver-doped bismuth tungstate heterojunction photocatalyst is 45-55 nm.
7. The silver-doped bismuth tungstate heterojunction photocatalyst as claimed in claim 5, wherein: the XRD spectrum of the silver-doped bismuth tungstate heterojunction photocatalyst shows that Bi is 2 WO 6 Characteristic peak, no impurity peak, and peak intensity at 28.3 DEG and 32.9 DEG relative to orthorhombic Bi 2 WO 6 Changes in the standard cards indicate Ag + Into Bi 2 WO 6 In the lattice space of or in place of Bi 3+ Cause Bi 2 WO 6 Causing lattice distortion.
8. The silver-doped bismuth tungstate heterojunction photocatalyst as claimed in claim 5, wherein: the molar concentration of Ag in the silver-doped bismuth tungstate heterojunction photocatalyst is 0.55-0.85%.
9. Use of the silver-doped bismuth tungstate heterojunction photocatalyst as claimed in any one of claims 5 to 8 in degradation of antibiotic-containing sewage.
10. Use according to claim 9, characterized in that: adding 40-50mg of the silver-doped bismuth tungstate heterojunction photocatalyst into the ciprofloxacin-containing sewage, wherein the concentration of the ciprofloxacin is 1-10mg/L, and the degradation rate of the ciprofloxacin is 60-90% when the sewage is illuminated for 180 min.
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