CN115463693A - Ag 2 O/isonicotinic acid-Bi composite photocatalyst and preparation and application thereof - Google Patents
Ag 2 O/isonicotinic acid-Bi composite photocatalyst and preparation and application thereof Download PDFInfo
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- CN115463693A CN115463693A CN202211310439.5A CN202211310439A CN115463693A CN 115463693 A CN115463693 A CN 115463693A CN 202211310439 A CN202211310439 A CN 202211310439A CN 115463693 A CN115463693 A CN 115463693A
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- isonicotinic acid
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940123317 Sulfonamide antibiotic Drugs 0.000 claims abstract description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
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- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 239000002135 nanosheet Substances 0.000 abstract description 2
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 14
- 229960004306 sulfadiazine Drugs 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 12
- 229960005404 sulfamethoxazole Drugs 0.000 description 11
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
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- 229910052797 bismuth Inorganic materials 0.000 description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 229940088710 antibiotic agent Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
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- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
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- 230000004580 weight loss Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
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Images
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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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
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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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- 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
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
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Abstract
The invention discloses Ag 2 The preparation method of the O/isonicotinic acid-Bi composite photocatalyst comprises the following steps: adding the isonicotinic acid-Bi complex into silver nitrate solution, and stirring to make Ag + Adsorbing on the surface of isonicotinic acid-Bi complex, performing hydrothermal reaction at 70-110 ℃, and obtaining Ag + With OH in aqueous solution ‑ Reacting to generate AgOH and decomposing to generate nano Ag 2 O, thereby preparing Ag 2 An O/isonicotinic acid-Bi composite photocatalyst. The isonicotinic acid-Bi complex is of a nanoscale lamellar structure. Hair brushObviously, a layer of Ag is loaded on the surface of the isonicotinic acid-Bi nanosheet under the hydrothermal condition 2 O nano-particles, preparing Ag with good photocatalytic activity 2 The O/isonicotinic acid-Bi composite photocatalyst can efficiently catalyze and degrade sulfonamide antibiotics in water environment.
Description
Technical Field
The invention belongs to the technical field of degradation of antibiotics, and particularly relates to Ag 2 A preparation method of an O/isonicotinic acid-Bi composite photocatalyst and application thereof in degrading sulfonamide antibiotics.
Background
Water pollution is an important environmental problem faced by countries in the world at present, and particularly with the development of modern industry and agriculture, organic compounds such as toxic dyes, antibiotics, endocrine disruptors and the like discharged into water have serious adverse effects on human health and the survival of aquatic organisms. The effect of the photocatalytic materials such as titanium dioxide and zinc oxide which are used in large quantities at present is not ideal. Therefore, in order to remove water pollutants efficiently, it is important to develop a novel catalyst having high catalytic activity.
In recent years, oxides and salts of metal bismuth (bismuth-based photocatalyst) have been found to have good photocatalytic activity, and have become a research hotspot in the fields of environmental water treatment, hydrogen production by photolysis, carbon dioxide photocatalytic reduction and the like. The bismuth-based photocatalyst has the advantage of being capable of fully utilizing visible light (sunlight) radiation to realize photocatalytic reaction. The absorption capacity of bismuth-based photocatalyst to visible light is far higher than that of the existing photocatalytic materials such as titanium dioxide and zinc oxide which are used in large quantity, so that the oxide and insoluble salt of bismuth are a kind of photocatalytic materials with wide application prospect.
In the prior art, bi is loaded on porous carbon synthesized by a bismuth-based metal organic framework 2 O 3 the/Bi ternary visible light catalyst is used for efficiently removing organic pollutants (novel carbon materials, 9.2020, volume 35, 5 th period, p 609-618) in water and degrading rhodamine B dye in water under visible light to study the photocatalytic performance of the materials. BiVO 4 Research on high-concentration sulfadiazine in photocatalytic degradation wastewater (energy environment protection 2020,34 (2): 30-36) simulates wastewater reaction for 4 hours by ultraviolet illumination with 10000lux intensity, the average removal rate of sulfadiazine is 90.97 percent, only the research is carried out on sulfadiazine, and when the sulfadiazine is recycled for 5 timesThe removal rate of (2) was 76.26%. At present, few reports about the photocatalytic activity of bismuth complexes and modified materials thereof are reported at home and abroad, and the research on the bismuth complexes is an important direction for developing a new generation of bismuth-based photocatalysts.
Disclosure of Invention
The invention aims to provide Ag 2 The O/isonicotinic acid-Bi composite photocatalyst and the preparation and the application thereof solve the problems of low efficiency and poor recycling effect of the existing photocatalyst in degrading sulfonamide antibiotics. The catalyst is a new catalyst, has good photocatalytic activity, cyclic usability and structural thermal stability, and can efficiently remove sulfonamide antibiotics in water.
In order to achieve the above purpose, the invention provides Ag 2 The preparation method of the O/isonicotinic acid-Bi composite photocatalyst comprises the following steps:
adding the isonicotinic acid-Bi complex into silver nitrate solution, and stirring to make Ag + Adsorbed on the surface of the isonicotinic acid-Bi complex; hydrothermal reaction at 70-110 deg.c to obtain Ag + With OH in aqueous solution - Reacting to generate AgOH and decomposing to generate nano Ag 2 O, thereby preparing Ag 2 O/isonicotinic acid-Bi composite photocatalyst;
Ag 2 the generation principle of O/isonicotinic acid-Bi is as follows: due to the pyridine nitrogen atom of isonicotinic acid to Ag + Has strong complexing ability, when the isonicotinic acid-Bi complex is added into silver nitrate solution and stirred at room temperature, the surface of the isonicotinic acid-Bi complex can adsorb a large amount of Ag + (ii) a Under hydrothermal conditions, ag + With OH in aqueous solution - Reacting to generate AgOH, and then rapidly decomposing the AgOH to generate the nano Ag under the heating condition of 70-110 DEG C 2 O; finally, a layer of Ag is formed on the surface of the isonicotinic acid-Bi complex 2 And O nanoparticles.
The isonicotinic acid-Bi complex has a structural formula as follows:
preferably, the concentration of the silver nitrate is (0.011-0.012) mol/L; the mass volume ratio of the isonicotinic acid-Bi complex to the silver nitrate solution is 0.2 g: 15mL.
Preferably, the temperature of the hydrothermal reaction is 90 ℃.
Preferably, the hydrothermal reaction time is 8h.
Preferably, the isonicotinic acid-Bi complex is prepared by adding bismuth trichloride and isonicotinic acid serving as raw materials into a solvent to react at 100 ℃.
Preferably, the solvent is an aprotic polar organic solvent and deionized water in a volume ratio of 1: 3, and the aprotic polar organic solvent is N, N-dimethylformamide.
Preferably, the mass volume ratio of the bismuth trichloride to the isonicotinic acid to the solvent is 3.15g to 2.46g to 40mL; in the preparation of the isonicotinic acid-Bi complex, the reaction time is 48 hours at 100 ℃.
The invention provides Ag as described 2 Ag prepared by preparation method of O/isonicotinic acid-Bi composite photocatalyst 2 O/isonicotinic acid-Bi composite photocatalyst.
Preferably, the isonicotinic acid-Bi complex is of a lamellar structure, and the Ag is 2 The surface of the O/isonicotinic acid-Bi composite photocatalyst contains Ag 2 And (3) O nanoparticles.
The invention provides Ag as described 2 The application of the O/isonicotinic acid-Bi composite photocatalyst in degrading sulfonamide antibiotics.
One kind of Ag of the present invention 2 The O/isonicotinic acid-Bi composite photocatalyst, and the preparation and the application thereof solve the problem that the existing photocatalyst can not rapidly remove sulfamethoxazole in water, and have the following advantages:
1. the isonicotinic acid-Bi complex synthesized under the hydrothermal condition is of a nanoscale lamellar structure.
2. The method loads a layer of Ag on the surface of the isonicotinic acid-Bi nanosheet under the hydrothermal condition 2 O nanoparticles to obtain Ag 2 O/isonicotinic acid-Bi composite photocatalyst.
3. Ag of the present invention 2 O/isonicotinic acid-Bi-90 (90 ℃ and Ag) + Product of the reaction) is repeatedAfter the photocatalyst is irradiated by visible light for 60min, the degradation rates of sulfadiazine and sulfamethoxazole in water are respectively 93% and 92%, and the degradation rate is still up to 91% after the photocatalyst is recycled for 4 times.
4. Ag of the present invention 2 The O/isonicotinic acid-Bi-90 composite photocatalyst has good thermal stability, has a very stable structure at 200 ℃, starts to be slowly decomposed when being heated to more than 200 ℃, and has only 10.97 percent of mass loss until 800 ℃.
Drawings
FIG. 1 is a schematic diagram of an isonicotinic acid-Bi complex prepared in example 1 of the present invention.
FIG. 2 shows Ag obtained in example 1 of the present invention 2 A physical diagram of the O/isonicotinic acid-Bi-90 composite photocatalyst.
FIG. 3 is an electron micrograph of the isonicotinic acid-Bi complex prepared in example 1 of the present invention.
FIG. 4 shows Ag obtained in example 1 of the present invention 2 An electron microscope picture of the O/isonicotinic acid-Bi-90 composite photocatalyst.
FIG. 5 shows Ag obtained in example 1 of the present invention 2 The absorption spectrogram of sulfadiazine catalytically degraded by O/isonicotinic acid-Bi-90 under different time is shown in the specification, wherein the abscissa is the absorption wavelength, and the ordinate is the absorbance.
FIG. 6 shows Ag obtained in example 1 of the present invention 2 An absorption spectrogram of the sulfamethoxazole catalytically degraded by the O/isonicotinic acid-Bi-90 at different time is shown, wherein the abscissa is the absorption wavelength, and the ordinate is the absorbance.
FIG. 7 shows Ag obtained in example 1 of the present invention 2 The thermal weight loss diagram of O/isonicotinic acid-Bi-90, wherein the abscissa is time, and the ordinate is mass fraction.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Ag 2 The preparation method of the O/isonicotinic acid-Bi nano composite photocatalyst comprises the following steps:
(1) Hydrothermal synthesis of isonicotinic acid-Bi complex
3.15g of bismuth trichloride (BiCl) were added in sequence to a 100mL beaker 3 ) 2.46g of isonicotinic acid (abbreviated as nic, molecular formula C) 6 H 5 NO 2 ) Then, 10mLN, N-dimethylformamide and 30mL of deionized water are added as solvents, and the raw materials are fully dissolved by magnetic stirring for 30min at room temperature; then transferring the mixed solution into a 100mL stainless steel reaction kettle with a polytetrafluoroethylene inner container, and reacting for 48h at 100 ℃;
and (3) post-treatment: and after the reaction is finished, naturally cooling to room temperature, filtering, collecting white precipitate, washing for 2 times by using deionized water, and drying in a drying box to obtain the white isonicotinic acid-Bi complex.
Isonicotinic acid-Bi complex Bi (nic) 2 (H 2 O) the molecular structure of Cl is as follows:
(2)Ag 2 hydrothermal synthesis of O/isonicotinic acid-Bi composite photocatalyst
Weighing 0.1g of silver nitrate in a 50mL beaker, and adding 15mL of deionized water for dissolving to obtain a silver nitrate solution; then 0.2g of the isonicotinic acid-Bi complex prepared in the step (1) is weighed and added into silver nitrate solution, and the mixture is magnetically stirred for 30min at room temperature to enable the isonicotinic acid-Bi complex to fully adsorb silver ions; transferring the mixed solution into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene inner container, and reacting for 8h at 90 ℃;
and (3) post-treatment: after the reaction is finished, naturally cooling to room temperature, carrying out vacuum filtration, collecting black products, washing with deionized water for 2 times, and drying in a drying oven at 50 ℃ to obtain black Ag 2 O/isonicotinic acid-Bi composite photocatalyst marked as Ag 2 O/isonicotinic acid-Bi-90 composite photocatalyst.
Example 2
Ag 2 Preparation of O/isonicotinic acid-BiA process substantially the same as example 1 except that:
reacting at 110 ℃ for 8h in the step (2); prepared Ag 2 O/isonicotinic acid-Bi composite photocatalyst marked as Ag 2 O/isonicotinic acid-Bi-110 composite photocatalyst.
Example 3
A preparation method of an Ag 2O/isonicotinic acid-Bi composite photocatalyst, which is substantially the same as that in example 1, except that:
reacting at 70 ℃ for 8h in the step (2); prepared Ag 2 O/isonicotinic acid-Bi composite photocatalyst marked as Ag 2 O/isonicotinic acid-Bi-70 composite photocatalyst.
As shown in FIG. 1, the object diagram of the isonicotinic acid-Bi complex prepared in example 1 of the present invention is shown.
As shown in FIG. 2, ag obtained in example 1 of the present invention 2 A physical diagram of the O/isonicotinic acid-Bi-90 composite photocatalyst.
As shown in FIG. 3, an electron micrograph of the isonicotinic acid-Bi complex prepared in example 1 of the present invention is shown. As is clear from FIG. 3, the scale is 2 μm, and the isonicotinic acid-Bi complex is a lamellar structure with a thickness of 10-20 nm.
As shown in FIG. 4, ag obtained in example 1 of the present invention 2 An electron microscope picture of the O/isonicotinic acid-Bi-90 composite photocatalyst. As is clear from FIG. 4, the scale is 200nm 2 The nano-particles on the surface of the O/isonicotinic acid-Bi-90 composite photocatalyst are Ag 2 O, having a size of about 10 to 30nm.
Experimental example 1 calculation of Ag 2 Band gap energy of O/isonicotinic acid-Bi composite photocatalyst
According to the test of the ultraviolet and visible diffuse reflection spectrum of the solid, the Ag is obtained by calculation 2 Band gap energy (E) of O/isonicotinic acid-Bi-90 g ) The minimum value is 2.70eV 2 O/isonicotinic acid-Bi-70 and Ag 2 Band gap energy (E) of O/isonicotinic acid-Bi-110 g ) 3.06eV and 2.85eV, respectively. Indicates that Ag is present 2 The O/isonicotinic acid-Bi-90 has higher utilization rate on light radiation.
Experimental example 2 detection of Ag 2 Reduction of sulfonamide antibiotics by O/isonicotinic acid-Bi-90 composite photocatalystEffect of solution
Ag prepared in example 1 2 The O/isonicotinic acid-Bi-90 composite photocatalyst is a catalyst, and the sulfadiazine and the sulfamethoxazole are degraded in a photocatalytic manner under the irradiation of visible light.
The apparatus used in this experiment was as follows:
the model of a xenon lamp manufacturer is CEL-HXF300, beijing Zhongzhijin source science and technology limited company;
the model of the double-beam ultraviolet visible spectrophotometer is TU-1901, beijing general analytical instruments, inc.
Ag 2 The O/isonicotinic acid-Bi-90 photocatalytic degradation sulfonamide antibiotic is used for setting an experimental group and a control group, and the specific experimental process is as follows: 50mL of sulfadiazine aqueous solution (20 mg/L, neutral) and 50mL of sulfamethoxazole aqueous solution (20 mg/L, neutral) are respectively weighed and added into 2 interlayer beakers filled with circulating condensed water, and then 50mgAg is respectively added 2 And (3) catalyzing by O/isonicotinic acid-Bi-90, respectively placing in a dark environment, stirring for 30min to enable the system to reach adsorption-desorption equilibrium, obtaining mixed liquor, respectively placing the mixed liquor under a 300W xenon lamp at room temperature, irradiating for 60min by using visible light for catalytic reaction (in a neutral environment), and marking as an experimental group. The control group contained no catalyst and the rest of the conditions were the same. In the reaction process, 3mL of solution is respectively taken from an experimental group and a control group at certain intervals, suspended matters are removed by centrifugation, a double-beam ultraviolet-visible spectrophotometer is used for testing antibiotics to obtain absorbance A, the concentration change of the sulfa antibiotic in the experimental group and the control group in the reaction is monitored, and the degradation rate of the antibiotics is obtained by calculation, wherein the specific calculation formula is as follows:
degradation rate = (A) 0 －A t )/A 0 ×100％
In the formula, A 0 Is the initial absorbance of the sulfa antibiotic before light exposure, A t The absorbance of the sulfanilamide antibiotic after t min of illumination is in direct proportion to the concentration of the sulfanilamide antibiotic.
As shown in FIG. 5, ag obtained in example 1 of the present invention 2 An absorption spectrogram of O/isonicotinic acid-Bi-90 for catalytically degrading sulfadiazine at different times, wherein the abscissa is absorption wavelength and the ordinate is absorption wavelengthAnd (4) luminosity.
As shown in FIG. 6, ag obtained in example 1 of the present invention 2 An absorption spectrogram of the sulfamethoxazole catalytically degraded by the O/isonicotinic acid-Bi-90 at different time is shown, wherein the abscissa is the absorption wavelength, and the ordinate is the absorbance. Ag prepared at 90 deg.C 2 The O/isonicotinic acid-Bi-90 is used as a catalyst, and as can be clearly seen from figures 5-6, the degradation rates of sulfadiazine and sulfamethoxazole after being irradiated by visible light for 60min reach 93 percent and 92 percent respectively.
Experimental example 3 Ag prepared at different temperatures was investigated 2 Catalytic activity of O/isonicotinic acid-Bi on sulfonamide antibiotics
Ag prepared at 70 ℃ in example 3 respectively 2 O/Isonicotinic acid-Bi-70, ag prepared at 110 ℃ in example 2 2 O/isonicotinic acid-Bi-110 is used as a catalyst, sulfadiazine and sulfamethoxazole are degraded in a photocatalytic manner under the irradiation of visible light, and other specific experimental conditions are the same as those of the experimental example 2.
And the verification result shows that: after 60min of visible light irradiation, ag 2 O/isonicotinic acid-Bi-110 and Ag 2 The degradation rate of O/isonicotinic acid-Bi-70 to sulfadiazine is 82 percent and 50 percent respectively; ag 2 O/isonicotinic acid-Bi-110 and Ag 2 The degradation rate of O/isonicotinic acid-Bi-70 to sulfamethoxazole is 56 percent and 23 percent respectively.
The Ag having the highest catalytic activity was prepared at 90 ℃ in comparison with Experimental example 2 2 O/Isonicotinic acid-Bi-90, followed by Ag prepared at 110 deg.C 2 O/isonicotinic acid-Bi-110, lowest Ag prepared at 70 deg.C 2 O/isonicotinic acid-Bi-70. Thus, ag 2 The O/isonicotinic acid-Bi-90 can efficiently catalyze and degrade the sulfonamide antibiotics.
Experimental example 4 detection of Ag after several cycles 2 Catalytic activity of O/isonicotinic acid-Bi on sulfonamide antibiotics
Ag with best photocatalytic performance in the experiment 2 O/isonicotinic acid-Bi-90 is subjected to catalyst recycling performance test, antibiotics sulfadiazine and sulfamethoxazole are respectively used as substrates, and after each photocatalytic experiment is finished, ag is collected by centrifugal treatment 2 The O/isonicotinic acid-Bi-90 catalyst is washed 3 times by using deionized water, and is dried in an oven at the temperature of 60 ℃ for repeated use. The rest are specificThe experimental conditions were the same as those of experimental example 2.
The experimental results show that: ag after 4 times of recycling 2 The degradation rates of the O/isonicotinic acid-Bi-90 catalyst on sulfadiazine and sulfamethoxazole are still respectively up to 91.2% and 90.6%.
Experimental example 5 detection of Ag 2 Stability of O/Isonicotinic acid-Bi-90
Ag using German relaxation-resistant STA2500 thermogravimetric analyzer 2 The stability of O/isonicotinic acid-Bi-90 was tested. The specific experimental process is as follows: slowly heating from room temperature to 800 ℃ in a nitrogen atmosphere, wherein the heating speed is 10 ℃/min, and measuring the mass loss at different temperatures in the heating process.
As shown in FIG. 7, ag obtained in example 1 of the present invention 2 The thermal weight loss diagram of O/isonicotinic acid-Bi-90, wherein the abscissa is time, and the ordinate is mass fraction. From FIG. 7, ag can be obtained 2 The O/isonicotinic acid-Bi-90 has a very stable structure at 200 ℃, and slowly decomposes when heated to above 200 ℃, but has only 10.97 percent of mass loss until 800 ℃.
Thus, the Ag prepared by the invention is subjected to a photocatalytic reaction at room temperature 2 The O/isonicotinic acid-Bi-90 catalyst has good stability, structural thermal stability and cyclic usability.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. Ag 2 The preparation method of the O/isonicotinic acid-Bi composite photocatalyst is characterized by comprising the following steps:
adding the isonicotinic acid-Bi complex into silver nitrate solution, and stirring to make Ag + Adsorbed on the surface of the isonicotinic acid-Bi complex; hydrothermal reaction at 70-110 deg.c to obtain Ag + With OH in aqueous solution - Reacting to generate AgOH and decomposing to generate nano Ag 2 O, thereby preparing Ag 2 O/isonicotinic acid-Bi composite photocatalyst;
the isonicotinic acid-Bi complex has a structural formula as follows:
2. ag according to claim 1 2 The preparation method of the O/isonicotinic acid-Bi composite photocatalyst is characterized in that the concentration of silver nitrate is (0.011-0.012) mol/L; the mass volume ratio of the isonicotinic acid-Bi complex to the silver nitrate solution is 0.2 g: 15mL.
3. Ag according to claim 1 2 The preparation method of the O/isonicotinic acid-Bi composite photocatalyst is characterized in that the temperature of the hydrothermal reaction is 90 ℃.
4. Ag according to claim 1 2 The preparation method of the O/isonicotinic acid-Bi composite photocatalyst is characterized in that the hydrothermal reaction time is 8 hours.
5. Ag according to claim 1 2 The preparation method of the O/isonicotinic acid-Bi composite photocatalyst is characterized in that the isonicotinic acid-Bi complex is prepared by adding bismuth trichloride and isonicotinic acid serving as raw materials into a solvent and reacting at 100 ℃.
6. The method of claim 5, wherein the solvent is the aprotic polar organic solvent and deionized water at a volume ratio of 1: 3, and the aprotic polar organic solvent is N, N-dimethylformamide.
7. The method for preparing the isonicotinic acid-Bi complex according to claim 5, wherein the mass-volume ratio of the bismuth trichloride to the isonicotinic acid to the solvent is 3.15 g: 2.46 g: 40mL; in the preparation of the isonicotinic acid-Bi complex, the reaction time is 48 hours at 100 ℃.
8. An Ag according to any one of claims 1-7 2 Ag prepared by preparation method of O/isonicotinic acid-Bi composite photocatalyst 2 O/isonicotinic acid-Bi composite photocatalyst.
9. Ag according to claim 8 2 The O/isonicotinic acid-Bi composite photocatalyst is characterized in that the isonicotinic acid-Bi complex is of a lamellar structure, and the Ag is 2 Surface of O/isonicotinic acid-Bi contains Ag 2 And (3) O nanoparticles.
10. An Ag according to claim 8 or 9 2 The application of the O/isonicotinic acid-Bi composite photocatalyst in degrading sulfonamide antibiotics.
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| JP2004330047A (en) * | 2003-05-06 | 2004-11-25 | Univ Kanazawa | Metal or metal oxide-carrying bismuth vanadate photocatalyst for photodecomposition of endocrine disruptor |
| CN106810580A (en) * | 2015-12-01 | 2017-06-09 | 宁波大学 | One kind 2,6- pyridinedicarboxylic acid bismuth complex photochemical catalysts |
| CN108786808A (en) * | 2018-06-26 | 2018-11-13 | 陕西科技大学 | A kind of Ag/BiO2-x/Bi2O3/Bi2O2.75Composite photo-catalyst and preparation method and application |
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| JP2004330047A (en) * | 2003-05-06 | 2004-11-25 | Univ Kanazawa | Metal or metal oxide-carrying bismuth vanadate photocatalyst for photodecomposition of endocrine disruptor |
| CN106810580A (en) * | 2015-12-01 | 2017-06-09 | 宁波大学 | One kind 2,6- pyridinedicarboxylic acid bismuth complex photochemical catalysts |
| CN108786808A (en) * | 2018-06-26 | 2018-11-13 | 陕西科技大学 | A kind of Ag/BiO2-x/Bi2O3/Bi2O2.75Composite photo-catalyst and preparation method and application |
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| CN115818695A (en) * | 2022-12-22 | 2023-03-21 | 西北师范大学 | Preparation method of litchi-shaped cuprous oxide/copper oxide nano-microspheres with tetrapeptidase activity |
| CN115818695B (en) * | 2022-12-22 | 2024-01-16 | 西北师范大学 | Preparation method of litchi-shaped cuprous oxide/cupric oxide nano microsphere with tetrazyme activity |
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