CN112121787B - Preparation method and application of monoclinic-phase bismuth tetroxide piezoelectric catalyst - Google Patents
Preparation method and application of monoclinic-phase bismuth tetroxide piezoelectric catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000000593 degrading effect Effects 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 5
- 239000012498 ultrapure water Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 4
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 229960002135 sulfadimidine Drugs 0.000 claims description 20
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 8
- 239000010865 sewage Substances 0.000 claims description 6
- VTSWSQGDJQFXHB-UHFFFAOYSA-N 2,4,6-trichloro-5-methylpyrimidine Chemical compound CC1=C(Cl)N=C(Cl)N=C1Cl VTSWSQGDJQFXHB-UHFFFAOYSA-N 0.000 claims description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 2
- 229940124530 sulfonamide Drugs 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 229940088710 antibiotic agent Drugs 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 22
- 238000006731 degradation reaction Methods 0.000 description 22
- 238000006555 catalytic reaction Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 6
- 229960004306 sulfadiazine Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
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- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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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
- C02F2101/40—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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention discloses a preparation method and application of a monoclinic phase bismuth tetroxide piezoelectric catalyst, which comprises the following steps: (1) Completely dispersing sodium bismuthate in pure water in a container containing polytetrafluoroethylene inner shell, and uniformly stirring and dispersing at a high speed to form a suspension; (2) Adding the suspension to 433 +/-5K for carrying out hydrothermal synthesis reaction for 10-15 h; (3) And repeatedly carrying out centrifugal washing on the obtained product through ultrapure water until the product is neutral, then repeatedly washing the product for a plurality of times through absolute ethyl alcohol, and then drying and drying the product to obtain the monoclinic-phase bismuth tetroxide piezoelectric catalyst. The piezoelectric catalyst synthesized by the method has high sample purity and good stability, m-Bi2O4 has higher piezoelectric catalytic activity under ultrasonic driving, and meanwhile, the piezoelectric catalyst has the advantages of simple structure, convenient synthesis, stability, safety, high activity, reaction under the conditions of normal temperature and normal pressure and the like, and shows better application prospect in the aspect of degrading antibiotics.
Description
Technical Field
The invention belongs to the technical field of water pollution, and particularly relates to monoclinic-phase bismuth tetroxide m-Bi 2 O 4 A catalyst and a preparation method thereof, and application of piezoelectric catalytic degradation antibiotics.
Background
The piezoelectric effect is a phenomenon that the polarization intensity of a material changes under the action of stress to generate potential difference. Mechanical energy generated by water flow, vibration and friction is visible everywhere in our life, can drive piezoelectric materials to deform to generate potential difference, and is clean and pollution-free energy. Therefore, the piezoelectric catalysis technology has wide application prospect in the aspect of purifying the environment due to the direct utilization of the low-frequency vibration energy of the environment.
At present, piezoelectric ceramics having a perovskite structure, an ultra-high piezoelectric coefficient, and an electromechanical coupling coefficient are the most used piezoelectric materials in microelectronic devices. The piezoelectric effect has been widely studied in the fields of piezoelectric sensors, electromechanical storage, and the like. Strain sensors and data storage devices utilize piezoelectric polarization to regulate local carrier transport of piezoelectric materials. The nanogenerator utilizes piezoelectric potentials to drive electron flow in a nanomaterial external circuit load. Meanwhile, the research of the piezoelectric catalysis technology in the environment mainly focuses on the aspects of pollutant degradation and hydrogen production by water cracking. The general mechanism of the piezo-catalytic reaction is that when a piezoelectric material is subjected to a stress provided by ultrasonic actuation, an electric field is formed within the material to promote charge separation, resulting in bending of the ribbon. Many semiconductor materials are thin and bend more easily under stress. The piezoelectric potential can induce contaminant molecules on the piezoelectric catalyst to undergo redox reactions via electron transfer.
Disclosure of Invention
The purpose of the invention is as follows: the technical problem to be solved by the invention is to provide a preparation method and application of a monoclinic-phase bismuth tetroxide piezoelectric catalyst, which has the remarkable advantages of piezoelectric catalytic degradation of sulfamethazine in sewage and higher catalytic efficiency.
The invention content is as follows: in order to solve the technical problems, the technical means adopted by the invention is as follows: the application of monoclinic phase bismuth tetroxide piezoelectric catalyst for degrading sulfadimidine in sewage comprises the following steps:
(1) Completely dispersing sodium bismuthate in pure water in a container containing polytetrafluoroethylene inner shell, and uniformly stirring and dispersing at a high speed to form a suspension;
(2) Adding the suspension obtained in the step (1) to 433 +/-5K, and carrying out hydrothermal synthesis reaction for 10 to 15h;
(3) And repeatedly carrying out centrifugal washing on a product obtained by the hydrothermal synthesis reaction through ultrapure water until the product is neutral, then repeatedly washing the product for a plurality of times through absolute ethyl alcohol, drying and drying the obtained washed precipitate, and obtaining the monoclinic-phase bismuth tetroxide piezoelectric catalyst.
Further, the rotation speed of centrifugal washing in the step (3) is 7500rpm, and the centrifugal time is 2-10min.
Further, 0.2 to 3g/L monoclinic phase bismuth oxide piezoelectric catalyst is added into sewage containing sulfamine methyl pyrimidine, and the anhydrous sulfamethazine is degraded in a dark environment and under ultrasonic vibration.
Further, the ultrasonic power is 180 to 600W, and the ultrasonic frequency is 20 to 50kHz.
Has the beneficial effects that: compared with the prior art, the invention has the following advantages: 1. the piezoelectric catalyst synthesized by the method has high sample purity and good stability, and m-Bi2O4 has higher piezoelectric catalytic activity under ultrasonic drive. 2. The m-Bi2O4 piezoelectric catalyst has the advantages of simple structure, convenience in synthesis, stability, safety, high activity, reaction under the conditions of normal temperature and normal pressure and the like, and shows a good application prospect in the aspect of degrading antibiotics.
Drawings
FIG. 1 is a drawing showing m-Bi prepared in example 1 of the present invention 2 O 4 X-ray diffraction pattern (XRD) of the catalyst.
FIG. 2 is a graph of m-Bi prepared in example 1 of the present invention 2 O 4 X-ray photoelectron spectroscopy (XPS) of the catalyst shows that bismuth in m-Bi2O4 is a mixed valence state of Bi (III) and Bi (V).
FIG. 3 shows m-Bi obtained in example 1 of the present invention and in comparative examples 1 and 2 2 O 4 、BiOCl、BaTiO 3 Catalyst versus SM degradation efficiency is plotted.
FIG. 4 shows m-B at different ultrasonic powers obtained in examples 1 and 2 of the present invention 2 O 4 Degradation efficiency of piezo-catalytic degradation SM is plotted versus time.
FIG. 5 shows m-B obtained in example 3 of the present invention 2 O 4 Three cycles of piezoelectric catalytic degradation of SMRing test comparison graph.
Detailed Description
The invention will be further elucidated with reference to the following description of an embodiment in conjunction with the accompanying drawing. It is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
The invention discloses a novel ultrasonic-driven typical narrow-bandgap semiconductor m-Bi2O4 nanosheet prepared by a hydrothermal method, and the novel ultrasonic-driven typical narrow-bandgap semiconductor m-Bi2O4 nanosheet has high piezoelectric catalytic degradation activity. Due to m-B 2 O 4 The nano material is non-centrosymmetric, and when the piezoelectric catalytic material is ultrasonically driven, an electric field is formed inside the material, so that dipole polarization is caused, and charge separation is accelerated. Driven by an internal electric field, holes migrate to m-B 2 O 4 The surface, as a direct oxidant, effectively degrades contaminants. Due to m-B 2 O 4 With proper conduction band position of the catalyst, the accumulated electrons can be utilized by dissolved oxygen to generate a large amount of superoxide radicals, some singlet oxygen and some hydroxyl radicals, which play a leading role in the degradation of pollutants. This results in m-B 2 O 4 Has good piezoelectric catalytic degradation performance on pollutants. The findings of this work highlight the further development of m-Bi 2 O 4 The piezoelectric catalyst has the prospect of restoring the environment under the ultrasonic drive. The piezoelectric catalytic degradation activity of the catalyst is far higher than that of the traditional mature high-efficiency piezoelectric catalyst BaTiO 3 And another bismuth-based catalyst, biOCl.
Example 1: m-Bi 2 O 4 Preparation and use of
(1) Hydrothermal synthesis method is adopted to prepare m-Bi 2 O 4 1.12 g sodium metabisulfite (NaBiO) which is a bismuth oxide with a composite valence state 3 ) Completely dispersed in 40 mL ultra pure water.
(2) And (3) placing the suspension in a stainless steel high-pressure reaction kettle with a 100 mL lining of polytetrafluoroethylene for hydro-thermal synthesis, wherein the reaction temperature is 433K, and the reaction time is 12 h.
(3) And (3) centrifugally washing a product after the hydrothermal reaction to be neutral by using ultrapure water, washing for 3 times by using ethanol, then placing the washed product in an oven at 328K, and drying for 12 h.
(4) And (4) carrying out piezoelectric catalytic degradation on sulfadiazine by using the catalyst obtained in the step (3). 50 mL sulfamethazine at an initial concentration of 10 mg/L in a 100 mL beaker, m-Bi 2 O 4 The catalyst was added in an amount of 0.06 g and sonicated under exclusion of light (frequency: 40 kHz, power 300W) at a temperature of 300K. After a reaction time of 2 h (sampling time points: 0min, 15 min,30 min,45 min,60 min,90 min,120 min), the concentration of sulfamethazine was measured using HPLC.
As is apparent from the characterization results of FIG. 1, all the diffractions are well indicated in Bi as evident from the XRD pattern of m-Bi2O4 2 O 4 The monoclinic phase of (A) has no other unnecessary miscellaneous peak, and the synthesized substance is very pure.
From the high resolution XPS spectrum of FIG. 2, m-Bi can be obtained 2 O 4 Bismuth in (b) is a mixed valence of Bi (iii) and Bi (v), and the peak of Bi (iii) is divided into two peaks having binding energies of 158.4 eV and 163.7 eV (the peak of Bi (v) is divided into two peaks having binding energies of 159.1 eV and 164.4 eV), which are the Bi (iii) state and the Bi (v) state, respectively.
m-Bi 2 O 4 The catalyst has good effect when being used for degrading sulfadimidine by piezoelectric catalysis. As can be seen from FIG. 3, the catalyst m-Bi is used 2 O 4 The sulfamethazine is subjected to piezoelectric catalysis, and the degradation rate of the sulfamethazine in 2 h is more than 90%.
Comparative example 1: biOCl piezoelectric catalytic degradation sulfadiazine
For comparative example 1, bisocl was used as the catalyst to degrade sulfamethazine with piezo catalysis. BiOCl has almost no piezoelectric catalytic degradation of sulfamethazine in 2 h under the same reaction conditions as example 1. Under the same conditions, m-Bi 2 O 4 The catalyst has higher catalytic activity than other bismuth-based (BiOCl) catalysts.
Comparative example 2: conventional piezoelectric catalyst barium titanate (BaTiO) 3 ) Piezoelectric catalytic degradation of sulfamethazine
For comparative example 2, a conventional piezoelectric catalyst BaTiO was used 3 And degrading sulfamethazine by piezoelectric catalysis. BaTiO under the same reaction conditions as in example 1 3 Almost no piezoelectric catalytic degradation of sulfamethazine was observed in 2 h. Under the same conditions, m-Bi 2 O 4 The catalyst is more traditional piezoelectric catalyst BaTiO 3 Has higher catalytic activity.
Example 2: m-Bi 2 O 4 Piezo-catalytic applications at different powers (180W, 450W, 600W)
(1) With m-Bi 2 O 4 Is used as a catalyst for degrading sulfa methyl pyrimidine by piezoelectric catalysis. The ultrasonic power was adjusted to 180W, other reaction conditions were the same as in example 1. As can be seen from FIG. 4, the catalyst m-Bi is present at an ultrasonic power of 180W 2 O 4 When the sulfamethazine is subjected to piezoelectric catalysis, the degradation rate of the sulfamethazine in 2 h is nearly 90 percent.
(2) With m-Bi 2 O 4 Is used as a catalyst for degrading sulfa methyl pyrimidine by piezoelectric catalysis. The ultrasonic power was adjusted to 450W, but under otherwise identical reaction conditions as in example 1. As can be seen from FIG. 4, the catalyst m-Bi is obtained when the ultrasonic power is 450W 2 O 4 When the piezoelectric catalyst is used for carrying out piezoelectric catalysis on the sulfadiazine, the degradation rate of the sulfadiazine in 15 min is obviously faster than that in 180W and 300W, and the degradation rate of the sulfadiazine in 2 h is nearly 90%.
(3) With m-Bi 2 O 4 Is used as a catalyst for degrading sulfa methyl pyrimidine by piezoelectric catalysis. The ultrasonic power was adjusted to 600W, but under otherwise identical reaction conditions as in example 1. As can be seen from FIG. 4, the catalyst m-Bi is obtained when the ultrasonic power is 600W 2 O 4 When the sulfamethazine is subjected to piezoelectric catalysis, the degradation rate of the sulfamethazine in 15 min is obviously faster than that in 180W and 300W, and the degradation rate of the sulfamethazine in 2 h is about 92%.
Example 3: m-Bi 2 O 4 Stability of recycling
(1) With m-Bi 2 O 4 To catalyzeThe agent, sulfadiazine is degraded by piezoelectric catalysis. Only the volume of the contaminant solution and the amount of the catalyst added were enlarged by 3 times (200 mL,240 mg), and the experiment was carried out under the same reaction conditions as in example 1.
(2) The catalyst after the reaction in (1) above was collected by centrifugation and dried, and then subjected to the second experiment, except that the volumes of the contaminant solution and the catalyst were changed to 100 mL and 120 mg, the experiment was performed under the same reaction conditions as in example 1.
(3) The catalyst after the reaction in (2) above was collected by centrifugation and dried, and then the third experiment was performed, except that the volumes of the contaminant solution and the catalyst were changed to 50 mL and 60 mg, and the experiment was performed under the same reaction conditions as in example 1.
From FIG. 5, it can be seen that after three consecutive cycles, m-Bi 2 O 4 Still has high piezoelectric catalytic activity.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (2)
1. The application of the monoclinic phase bismuth tetroxide piezoelectric catalyst is characterized in that: the preparation method for degrading sulfamethazine in sewage comprises the following steps:
(1) Completely dispersing sodium bismuthate in pure water in a container containing polytetrafluoroethylene inner shell, and uniformly stirring and dispersing at a high speed to form a suspension;
(2) Heating the suspension obtained in the step (1) to 433 +/-5K, and carrying out hydrothermal synthesis reaction for 10 to 15h;
(3) Repeatedly carrying out centrifugal washing on a product obtained by the hydrothermal synthesis reaction through ultrapure water until the product is neutral, then repeatedly washing the product for a plurality of times through absolute ethyl alcohol, drying and drying the obtained washed precipitate, and obtaining the monoclinic-phase bismuth tetroxide piezoelectric catalyst;
adding 0.2-3 g/L of monoclinic phase bismuth oxide piezoelectric catalyst into sewage containing sulfamine methyl pyrimidine, and degrading the sulfamethazine in the sewage in a dark environment under ultrasonic vibration; the ultrasonic power is 180 to 600W, and the ultrasonic frequency is 20 to 50kHz.
2. Use of a monoclinic phase bismuth tetroxide piezoelectric catalyst according to claim 1, characterized in that: the rotation speed of centrifugal washing in the step (3) is 7500rpm, and the centrifugal time is 2-10min.
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| CN108273492A (en) * | 2018-04-01 | 2018-07-13 | 云南大学 | A kind of bismuth oxide/bismuth tetroxide heterojunction photocatalyst and its preparation method and purposes |
| CN108906090A (en) * | 2018-07-20 | 2018-11-30 | 苏州科技大学 | A kind of optic catalytic composite material and its preparation method and application with p-n heterojunction |
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| CN108273492A (en) * | 2018-04-01 | 2018-07-13 | 云南大学 | A kind of bismuth oxide/bismuth tetroxide heterojunction photocatalyst and its preparation method and purposes |
| CN108906090A (en) * | 2018-07-20 | 2018-11-30 | 苏州科技大学 | A kind of optic catalytic composite material and its preparation method and application with p-n heterojunction |
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