CN111054413B - Ternary composite multi-effect photocatalyst and preparation method thereof - Google Patents
Ternary composite multi-effect photocatalyst and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 239000011206 ternary composite Substances 0.000 title claims abstract description 17
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims abstract description 29
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- NTHXOOBQLCIOLC-UHFFFAOYSA-N iohexol Chemical compound OCC(O)CN(C(=O)C)C1=C(I)C(C(=O)NCC(O)CO)=C(I)C(C(=O)NCC(O)CO)=C1I NTHXOOBQLCIOLC-UHFFFAOYSA-N 0.000 claims description 15
- 229960001025 iohexol Drugs 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 10
- 230000000593 degrading effect Effects 0.000 claims description 10
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims description 9
- 238000004729 solvothermal method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 9
- 238000002156 mixing Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 15
- 229910021642 ultra pure water Inorganic materials 0.000 description 15
- 239000012498 ultrapure water Substances 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000012452 mother liquor Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal 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
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention discloses a ternary composite multiple-effect photocatalyst and a preparation method thereof, wherein the ternary composite multiple-effect photocatalyst is prepared from Co 3 O 4 、Bi 2 O 2 CO 3 And g-C 3 N 4 The three are prepared by compounding, and the preparation method is that the hydrothermal synthesis method is utilized to synthesize the Bi with the lamellar 2D structure with large surface area 2 O 2 CO 3 Slicing, and subjecting the 2D structure g-C to ultrasonic treatment 3 N 4 Bi of 2D structure 2 O 2 CO 3 Mixing the slices uniformly, adding Co 2+ The solution is finally oxidized again by hydrothermal synthesis 2+ Formation of Co 3 O 4 Point load on 2D/2D Bi 2 O 2 CO 3 /g‑C 3 N 4 The ternary composite multi-effect photocatalyst is obtained, and the ternary heterojunction material has excellent persulfate activation and pollutant photocatalytic degradation capacity, high degradation efficiency and environmental friendliness.
Description
Technical Field
The invention relates to a composite photocatalyst and a preparation method and application thereof, in particular to a ternary composite multi-effect photocatalyst and a preparation method and application thereof, belonging to the technical field of nano material synthesis.
Background
Under the era background of rapid development of science and technology, over-development and utilization of energy sources such as petroleum and coal and the like and damage to the environment caused by heavily polluted industries are caused, so that pollution-free and renewable energy sources are urgently needed. The photocatalysis technology has the advantages of clean and renewable solar energy as an energy source, and the application fields comprise pollution removal, catalytic hydrogen production and the like which are related to the environment, so that the photocatalysis technology becomes an important technical means for improving the environment in the visual field of people. The persulfate activation technology is an environmental pollution treatment technology which has just emerged in recent years. SO generated during persulfate activation 4 - Half-life ratio of OH to O 2 The half-life period of the compound is long, and the standard oxidation-reduction potential reaches 2.5eV-3.1eV, so that the compound has the characteristics of lasting action time, strong oxidation capacity and the like, and the application of the compound in the field of environmental protection becomes possible. Conventional TiO 2 The visible light part occupying most of the solar energy can not be absorbed, the recombination efficiency of photogenerated electrons and holes is high, and the time for degrading pollutants by photocatalysis is long, so that the photocatalysis is not beneficial to engineering application.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a ternary heterojunction photocatalyst which has excellent persulfate activation and capacity of degrading pollutants through photocatalysis, high degradation efficiency and is environment-friendly, and the second purpose of the invention is to provide a preparation method of the photocatalyst.
The technical scheme is as follows: the ternary composite multiple-effect photocatalyst of the invention is prepared from Co 3 O 4 、Bi 2 O 2 CO 3 And g-C 3 N 4 The three are prepared by compounding.
Further, Co element, Bi element and g-C 3 N 4 The mass ratio of (A) to (B) is 1-4: 8-24: 1.
g-C of the invention 3 N 4 The preparation method comprises the following steps:
weighing melamine, heating the sample to 500-550 ℃ at the heating rate of 3-5 ℃/min under nitrogen atmosphere, and keeping the temperature for roasting for 4-6 h.
The preparation method of the ternary composite multiple-effect photocatalyst comprises the following steps:
(1) promotion of Bi (NO) by surfactants 3 ) 3 `5H 2 O forms ionic solution A and Bi with 2D structure by hydrothermal reaction under acidic condition 2 O 2 CO 3 A sheet;
(2) dissolving cobalt acetate tetrahydrate in a mixed solution of absolute ethyl alcohol and water, and performing ultrasonic treatment to form a mixed solution containing uniform Co 2+ Dispersion liquid B of (1);
(3) adding the dispersion liquid B into a mixed solution of absolute ethyl alcohol and water, and adding Bi with a 2D structure 2 O 2 CO 3 g-C of flake and 2D structures 3 N 4 Obtaining a dispersion liquid C with cobalt ions dispersed on the 2D/2D sheet layer by a solvothermal method;
(4) the dispersion C was reacted by a solvothermal method.
Further, the surfactant in the step (1) is cetyl ammonium bromide, cetyl ammonium bromide and Bi (NO) 3 ) 3 `5H 2 The mass ratio of O is 1: 4-10.
Further, the acidic condition in the step (1) is that nitric acid and Bi (NO) are mixed in nitric acid solution 3 ) 3 `5H 2 The molar ratio of O is 30-60: 1.
further, the hydrothermal reaction in the step (1) is carried out at 50-100 ℃.
Further, Co in the dispersion B of the step (3) 2+ Absolute ethyl alcohol, Bi of 2D structure 2 O 2 CO 3 g-C of flake and 2D structures 3 N 4 The ratio of (A) to (B) is 4 g: 10-15 ml: 8 g-24 g: 1g of the total weight of the composition.
Further, the solvothermal method in the step (3) is carried out at the temperature of 60-80 ℃.
Further, the solvothermal method in the step (4) is carried out at 100-200 ℃.
Preferably, the hydrothermal reaction in step (1) is carried out in a stainless steel autoclave.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: co preparation by simple rapid hydrothermal synthesis method and solvothermal method 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 The ternary composite multi-effect photocatalyst shows excellent persulfate activation and pollutant photocatalytic degradation capability under simulated sunlight irradiation; g-C 3 N 4 The introduction of the method solves the problems that the reactions are easy to influence each other and the like, and improves the specific surface area and the absorption utilization rate of sunlight; is nontoxic and harmless, and meets the environment-friendly requirement.
The preparation method is simple, the raw materials are easy to obtain, and the energy consumption and the preparation cost are greatly reduced; is convenient for batch production.
Drawings
FIG. 1 shows Co of the present invention 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 An X-ray diffraction (XRD) pattern of the ternary composite multi-effect photocatalyst;
FIG. 2 shows Co of the present invention 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 A Fourier infrared (FT-IR) diagram of the three-way composite multi-effect photocatalyst;
FIG. 3(a) shows Bi 2 O 2 CO 3 (2D) FIG. 3(b) is a Scanning Electron Microscope (SEM) picture of (C), Co 3 O 4 /Bi 2 O 2 CO 3 FIG. 3(c) is a Scanning Electron Microscope (SEM) image of Co of the present invention 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 Scanning Electron Microscope (SEM) picture of ternary composite multi-effect photocatalyst, and 3(d) is marked Co 3 O 4 Dot size Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 The Scanning Electron Microscope (SEM) picture of the ternary composite multi-effect photocatalyst, 3(e) is Co of the invention 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 An Element Distribution (EDS) diagram of the ternary complex multi-effect photocatalyst;
FIG. 4 shows a ternary composite multi-effect material Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 The effect graph of photocatalysis and persulfate activation degradation of the iohexol aqueous solution with the concentration of 20mg/L under the irradiation of simulated sunlight.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
Preparation of g-C 3 N 4 Catalyst:
preparation of g-C by direct pyrolysis of 10g melamine in a tubular furnace under the protection of nitrogen 3 N 4 And the mixture is kept for standby. The heating rate of the pyrolysis is 3 ℃/min, the constant temperature is 550 ℃, and the calcination time is 4 h.
II, preparing Bi 2 O 2 CO 3 (2D) Catalyst and process for preparing same
1. Nitric acid and Bi (NO) 3 ) 3 `5H 2 O is obtained by mixing the following components in a molar ratio of 30: 1 dissolving bismuth nitrate in nitric acid, stirring for 20min, adding hexadecylammonium bromide, hexadecylammonium bromide and Bi (NO) 3 ) 3 `5H 2 And the mass ratio of O is 1:4 to obtain an ionic solution A, and then sodium carbonate powder with the mass of 0.01mol is added and stirred for 30min to react to generate bismuth oxycarbonate.
2. Placing the reacted solution in a stainless steel autoclave, carrying out thermal reaction at 50 ℃ for 24h, naturally cooling to room temperature after the reaction is finished, respectively alternately washing 3 times by ultrapure water and absolute ethyl alcohol, and drying at constant temperature of 50 ℃ to obtain the two-dimensional flaky Bi 2 O 2 CO 3 。
Thirdly, preparation of Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 Multifunctional catalytic material
1. Dissolving cobalt acetate tetrahydrate in water to prepare 0.2M cobalt ion mother liquor, and dispersing the mother liquor in ultrapure water absolute ethyl alcohol to obtain dispersion liquid B, wherein Co in the dispersion liquid B 2+ Absolute ethyl alcohol, Bi of 2D structure 2 O 2 CO 3 g-C of flake and 2D structures 3 N 4 The ratio of (A) to (B) is 4 g: 10 ml: 8 g: 1g of the total weight of the composition.
2. 0.001g of g-C prepared in (a) 3 N 4 (2D) And 0.024g of Bi prepared in step two 2 O 2 CO 3 (2D) Adding into the dispersion solution B to obtain dispersion solution C, performing ultrasonic treatment at 80 deg.C for 3 hr, and mixing cobalt ion and Bi 2 O 2 CO 3 And g-C 3 N 4 And (4) uniformly mixing.
3. Placing the solution after ultrasonic treatment in a stainless steel autoclave, carrying out constant temperature thermal reaction for 3h at 150 ℃, alternately washing for 3 times by using ultrapure water and absolute ethyl alcohol after the reaction is finished, and drying for 12h at constant temperature of 60 ℃ to obtain Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 A composite material.
Example 2
Preparation of Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 Catalytic material
Preparation of g-C 3 N 4 Catalyst:
tubular furnace for preparing g-C by directly pyrolyzing 10g of melamine under nitrogen protection 3 N 4 And the mixture is kept for standby. The heating rate of the pyrolysis is 5 ℃/min, the constant temperature is 500 ℃, and the calcination time is 6 h.
II, preparing Bi 2 O 2 CO 3 (2D) Catalyst and process for preparing same
1. Nitric acid and Bi (NO) 3 ) 3 `5H 2 O is prepared according to the molar ratio of 60: 1 dissolving bismuth nitrate in nitric acid, stirring for 20min, adding hexadecylammonium bromide, hexadecylammonium bromide and Bi (NO) 3 ) 3 `5H 2 And the mass ratio of O is 1:10 to obtain an ionic solution A, and then sodium carbonate powder with the mass of 0.01mol is added and stirred for 30min to react to generate bismuth oxycarbonate.
2. Placing the reacted solution in a stainless steel autoclave, carrying out thermal reaction at 80 ℃ for 24h, naturally cooling to room temperature after the reaction is finished, respectively alternately washing 3 times with ultrapure water and absolute ethyl alcohol, and drying at constant temperature of 50 ℃, namelyTo obtain two-dimensional flaky Bi 2 O 2 CO 3 。
Thirdly, preparation of Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 Multifunctional catalytic material
1. Dissolving cobalt acetate tetrahydrate in water to prepare cobalt ion mother liquor with the concentration of 0.2M, and dispersing the mother liquor in ultrapure water absolute ethyl alcohol to obtain dispersion liquid B, wherein Co in the dispersion liquid B 2+ Absolute ethyl alcohol, Bi of 2D structure 2 O 2 CO 3 g-C of flake and 2D structures 3 N 4 The ratio of (b) is 4 g: 15 ml: 24 g: 1g of the total weight of the composition.
2. 0.001g of (a) prepared g-C 3 N 4 (2D) And 0.024g of Bi prepared in step two 2 O 2 CO 3 (2D) Adding into the dispersion B to obtain dispersion C, performing ultrasonic treatment at 60 deg.C for 3 hr, and mixing cobalt ion and Bi 2 O 2 CO 3 And g-C 3 N 4 And (4) uniformly mixing.
3. Placing the solution after ultrasonic treatment in a stainless steel autoclave, carrying out a constant temperature thermal reaction at 100 ℃ for 3h, alternately washing with ultrapure water and absolute ethyl alcohol for 3 times after the reaction is finished, and drying at a constant temperature of 60 ℃ for 12h to obtain Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 A composite material.
Example 3
Preparation of Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 Catalytic material
Preparation of g-C 3 N 4 Catalyst:
tubular furnace for preparing g-C by directly pyrolyzing 10g of melamine under nitrogen protection 3 N 4 And keeping the mixture for standby. The heating rate of the pyrolysis is 4 ℃/min, the constant temperature is 530 ℃, and the calcination time is 5 h.
II, preparing Bi 2 O 2 CO 3 (2D) Catalyst and process for preparing same
1. Nitric acid and Bi (NO) 3 ) 3 `5H 2 O is prepared according to the molar ratio of 45: 1 dissolving bismuth nitrate in nitric acid, stirring for 20min, adding hexadecyl ammonium bromide and decaHexaalkyl ammonium bromide and Bi (NO) 3 ) 3 `5H 2 And the mass ratio of O is 1:7 to obtain an ionic solution A, and then adding sodium carbonate powder with the mass amount of 0.01mol into the ionic solution A, and stirring the mixture for 30min to react to generate the bismuth oxycarbonate.
2. Placing the reacted solution in a stainless steel autoclave, carrying out thermal reaction at 100 ℃ for 24h, naturally cooling to room temperature after the reaction is finished, respectively alternately washing 3 times by ultrapure water and absolute ethyl alcohol, and drying at constant temperature of 50 ℃ to obtain the two-dimensional flaky Bi 2 O 2 CO 3 。
Thirdly, preparation of Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 Multifunctional catalytic material
1. Dissolving cobalt acetate tetrahydrate in water to prepare cobalt ion mother liquor with the concentration of 0.2M, and dispersing the mother liquor in ultrapure water absolute ethyl alcohol to obtain dispersion liquid B, wherein Co in the dispersion liquid B 2+ Absolute ethyl alcohol, Bi of 2D structure 2 O 2 CO 3 g-C of flake and 2D structures 3 N 4 The ratio of (A) to (B) is 4 g: 12 ml: 15 g: 1g of the total weight of the composition.
2. 0.001g of g-C prepared in (a) 3 N 4 (2D) And 0.024g of Bi prepared in step two 2 O 2 CO 3 (2D) Adding into the dispersion solution B to obtain dispersion solution C, performing ultrasonic treatment at 70 deg.C for 3 hr, and mixing cobalt ion and Bi 2 O 2 CO 3 And g-C 3 N 4 And (4) uniformly mixing.
3. Placing the solution after ultrasonic treatment in a stainless steel autoclave, carrying out constant temperature thermal reaction at 200 ℃ for 3h, alternately washing with ultrapure water and absolute ethyl alcohol for 3 times after the reaction is finished, and drying at constant temperature of 60 ℃ for 12h to obtain Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 A composite material.
Example 4
Preparing an iohexol simulated solution:
dissolving 50mg of iohexol white powder in 50ml of ultrapure water, and uniformly stirring to prepare iohexol mother liquor with the concentration of 1g/L for later use.
In each degradation experiment, 1ml of iohexol mother liquor is taken in a 50ml quartz colorimetric tube, and is diluted to 50ml by adding water to prepare an experiment solution with the concentration of 20 mg/L. Then 50mg of catalyst powder is added, the mixture is put into a photocatalytic reactor, 1000W Xe is used as a simulated sunlight source to react for 30min under the dark condition, and finally 0.0357g of sodium persulfate powder is added to start the reaction and degradation.
Comparative example 1
Preparation of Co 3 O 4 /Bi 2 O 2 CO 3
Firstly, preparing Bi 2 O 2 CO 3 (2D) Catalyst and process for preparing same
1. Dissolving 0.970g of bismuth nitrate in 80ml of 1mol/L nitric acid, stirring for 20min to obtain an ionic solution A, adding sodium carbonate powder with the amount of 0.01mol of substance, and stirring for 30min to react to generate bismuth oxycarbonate.
2. Placing the reacted solution in a stainless steel autoclave, carrying out thermal reaction at 60 ℃ for 24h, naturally cooling to room temperature after the reaction is finished, respectively alternately washing 3 times by ultrapure water and absolute ethyl alcohol, and drying at constant temperature of 50 ℃ to obtain the two-dimensional flaky Bi 2 O 2 CO 3 。
II, preparing Co 3 O 4 /Bi 2 O 2 CO 3 Catalyst and process for preparing same
1. Dissolving cobalt acetate tetrahydrate in water to prepare a cobalt ion mother liquor with a certain substance amount concentration of 0.2M, and dispersing 1.2ml of the mother liquor in 15ml of ultrapure water and 15ml of absolute ethyl alcohol to obtain a dispersion liquid B.
2. Mixing 0.024g of prepared Bi 2 O 2 CO 3 (2D) Adding into the dispersion liquid B to obtain dispersion liquid D, performing ultrasonic treatment at 60-80 deg.C for 3 hr, and mixing cobalt ions with Bi 2 O 2 CO 3 And (4) uniformly mixing.
3. Placing the solution after ultrasonic treatment in a stainless steel autoclave, carrying out constant temperature thermal reaction at 150 ℃ for 3h, alternately washing with ultrapure water and absolute ethyl alcohol after the reaction is finished, and drying at 60 ℃ for 12h to obtain Co 3 O 4 /Bi 2 O 2 CO 3 A composite material.
Comparative example 2
Preparation of Bi 2 O 2 CO 3 /g-C 3 N 4 Catalyst and process for preparing same
Preparation of g-C 3 N 4 Catalyst:
preparation of g-C by direct pyrolysis of 10g melamine in a tubular furnace under the protection of nitrogen 3 N 4 And keeping the mixture for standby. The constant temperature of the pyrolysis is 550 ℃, and the calcination time is 4 h.
II, preparing Bi 2 O 2 CO 3 (2D) Catalyst and process for preparing same
Dissolving 0.970g of bismuth nitrate in 80ml of 1mol/L nitric acid, stirring for 20min to obtain an ionic solution A, adding sodium carbonate powder with the amount of 0.01mol of substance, and stirring for 30min to react to generate the bismuthyl carbonate. Placing the reacted solution in a stainless steel autoclave, carrying out thermal reaction at 60 ℃ for 24h, naturally cooling to room temperature after the reaction is finished, respectively alternately washing 3 times by ultrapure water and absolute ethyl alcohol, and drying at constant temperature of 50 ℃ to obtain the two-dimensional flaky Bi 2 O 2 CO 3 。
Thirdly, preparing Bi 2 O 2 CO 3 /g-C 3 N 4 Catalyst and process for preparing same
Mixing 0.024g of prepared Bi 2 O 2 CO 3 (2D) And 0.001g of g-C prepared 3 N 4 (2D) Adding into 15ml ultrapure water +15ml anhydrous ethanol to obtain dispersion E, performing ultrasonic treatment at 60-80 deg.C for 3 hr, mixing g-C 3 N 4 And Bi 2 O 2 CO 3 And (4) uniformly mixing.
The concentration of iohexol at each time point was determined using an agilent 1200 liquid chromatograph.
The invention utilizes the invention to utilize X-ray diffraction (XRD) and Fourier infrared (FT-IR) to Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 The successful preparation of the ternary composite multi-effect photocatalyst and the persulfate activator is determined, and Bi appears in an XRD (X-ray diffraction) pattern as shown in figure 1-2 2 O 2 CO 3 And Co 3 O 4 The characteristic peak of the composite material is matched with a standard card (JCPDS card No.41-1448), and g-C appears in the FT-IR spectrum of the composite material 3 N 4 Characteristic peak and g-C 3 N 4 The characteristic peaks measured by FT-IR spectrum are coincident. Three-phase materialMaterial Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 The preparation is successful.
Co in the invention 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 The morphology of the ternary complex multi-effect multifunctional catalyst was determined by Scanning Electron Microscopy (SEM), and FIG. 3(a) is Bi 2 O 2 CO 3 (2D) From the figure, it can be seen that Bi is produced 2 O 2 CO 3 The surface area is large, and a sheet structure is presented; FIG. 3(b) shows Co 3 O 4 /Bi 2 O 2 CO 3 Composite material, Co being visible from the figure 3 O 4 The nano particles are uniformly dispersed in the flaky Bi 2 O 2 CO 3 A surface; FIG. 3(c) shows Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 The g-C can be seen from the figure 3 N 4 And Bi 2 O 2 CO 3 Closely bonded, and Co 3 O 4 The nano-dots are in g-C 3 N 4 (2D) And Bi 2 O 2 CO 3 (2D) The upper distribution is uniform, and FIG. 3(d) shows Co 3 O 4 Dot size Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 A three-element composite multi-effect multifunctional catalyst material. Fig. 3(e) is a composite Element Distribution (EDS) diagram.
FIG. 4 is Co 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 And (3) comparing the degradation effects of the ternary composite multi-effect material under different conditions. It can be seen that Co is present at the same time 3 O 4 /Bi 2 O 2 CO 3 /g-C 3 N 4 1000W Xe, 3mM persulfate.
On the other hand, by two-dimensional (2D) carbon nitride (g-C) 3 N 4 ) Coupling Co 3 O 4 /Bi 2 O 2 CO 3 The heterojunction structure is formed to further inhibit recombination of photo-generated electron-hole pairs, thereby making the structure extremely compactGreatly prolongs the service life of the photo-generated electrons and further improves the activity of the photo-catalytic performance of the photo-generated electrons. Is simultaneously vertically inserted into Bi 2 O 2 CO 3 In the above way, the chemical reaction is separated without mutual influence.
Claims (9)
1. The application of the ternary composite multi-effect photocatalyst for degrading iohexol after being activated by sulfate is characterized in that: the ternary composite multiple-effect photocatalyst is prepared from Co 3 O 4 、Bi 2 O 2 CO 3 And g-C 3 N 4 The preparation method comprises the following steps:
(1) promotion of Bi (NO) by hexadecylammonium bromide 3 ) 3` 5H 2 O forms ionic solution A and Bi with 2D structure by hydrothermal reaction under acidic condition 2 O 2 CO 3 A sheet;
(2) dissolving cobalt acetate tetrahydrate in a mixed solution of absolute ethyl alcohol and water, and performing ultrasonic treatment to form a mixed solution containing uniform Co 2+ Dispersion liquid B of (1);
(3) adding the dispersion liquid B into a mixed solution of absolute ethyl alcohol and water, and adding Bi with a 2D structure 2 O 2 CO 3 g-C of flake and 2D structures 3 N 4 Obtaining a dispersion liquid C with cobalt ions dispersed on the 2D/2D sheet layer by a solvothermal method;
(4) the dispersion C was reacted by a solvothermal method.
2. The application of the three-element composite multi-effect photocatalyst for degrading iohexol after being activated by sulfate according to claim 1 is characterized in that: the Co element, the Bi element and g-C 3 N 4 The mass ratio of (A) to (B) is 1-4: 8-24: 1.
3. The application of the three-element composite multi-effect photocatalyst for degrading iohexol after being activated by sulfate according to claim 1 is characterized in that: the g to C 3 N 4 The preparation method comprises the following steps:
weighing melamine, heating the sample to 500-550 ℃ at the heating rate of 3-5 ℃/min under nitrogen atmosphere, and keeping the temperature for roasting for 4-6 h.
4. The application of the three-element composite multi-effect photocatalyst for degrading iohexol after being activated by sulfate according to claim 1 is characterized in that: the hexadecyl ammonium bromide and Bi (NO) in the step (1) 3 ) 3` 5H 2 The mass ratio of O is 1: 4-10.
5. The application of the three-element composite multi-effect photocatalyst for degrading iohexol after being activated by sulfate according to claim 1 is characterized in that: the acidic condition in the step (1) is that the nitric acid is in nitric acid solution, and the nitric acid is mixed with Bi (NO) 3 ) 3` 5H 2 The molar ratio of O is 30-60: 1.
6. the application of the three-element composite multi-effect photocatalyst for degrading iohexol after being activated by sulfate according to claim 1 is characterized in that: the hydrothermal reaction in the step (1) is carried out at 50-100 ℃.
7. The application of the three-element composite multi-effect photocatalyst for degrading iohexol after being activated by sulfate according to claim 1 is characterized in that: co in the dispersion liquid B in the step (3) 2+ Absolute ethyl alcohol, Bi of 2D structure 2 O 2 CO 3 g-C of flake and 2D structure 3 N 4 The ratio of (b) is 4 g: 10-15 ml: 8 g-24 g: 1g of the total weight of the composition.
8. The application of the three-element composite multi-effect photocatalyst for degrading iohexol after being activated by sulfate according to claim 1 is characterized in that: the solvothermal method in the step (3) is carried out at the temperature of 60-80 ℃.
9. The application of the ternary complex multi-effect photocatalyst in the degradation of iohexol after being activated by sulfate according to claim 1 is characterized in that: the solvothermal method in the step (4) is carried out at 100-200 ℃.
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