CN115636440A - In + doped (001) crystal face exposed oxygen-containing vacancy BiOCl nanosheet and preparation method thereof - Google Patents
In + doped (001) crystal face exposed oxygen-containing vacancy BiOCl nanosheet and preparation method thereof Download PDFInfo
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000002135 nanosheet Substances 0.000 title claims abstract description 87
- 239000013078 crystal Substances 0.000 title claims abstract description 77
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000001301 oxygen Substances 0.000 title claims abstract description 59
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 30
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 15
- 239000001103 potassium chloride Substances 0.000 claims abstract description 15
- 229910052738 indium Inorganic materials 0.000 claims abstract description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- 239000002244 precipitate Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052753 mercury Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- HCJLVWUMMKIQIM-UHFFFAOYSA-M sodium;2,3,4,5,6-pentachlorophenolate Chemical compound [Na+].[O-]C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl HCJLVWUMMKIQIM-UHFFFAOYSA-M 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000001678 irradiating effect Effects 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 239000000575 pesticide Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002055 nanoplate Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003403 water pollutant Substances 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
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- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The present invention discloses an In + A (001) crystal face-doped BiOCl nanosheet visible light photocatalyst with an exposed oxygen-containing vacancy and a preparation method thereof. The method is characterized in that bismuth nitrate, indium nitrate and potassium chloride are used as precursors (the mass ratio of indium element to bismuth element is 1-5 o C～180 o C reacting for 10-30 hours to obtain In 3+ Exposing the BiOCl nanosheet by doping (001) crystal face, and irradiating the obtained sample by ultraviolet light for 1-4 hours to obtain In + The (001) doped crystal face exposes the BiOCl nano-sheet containing oxygen vacancy, the size of the BiOCl nano-sheet is less than 200 nm, and the thickness of the BiOCl nano-sheet is 15-25 nm. In (001) crystal face exposed BiOCl nanosheet prepared by using method disclosed by the invention + In the presence of oxygen vacancies, indium replaces bismuthCan effectively degrade the sodium pentachlorophenol serving as a pesticide under light. The method has the advantages of simple process, low cost, environmental friendliness, high yield, suitability for large-scale production, accordance with actual production requirements and great application potential.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic materials, and particularly relates to In + A (001) -doped crystal face exposed oxygen-containing vacancy BiOCl nanosheet and a preparation method thereof.
Background
BiOCl is paid much attention because of having a unique layered structure, and is applied to the field of liquid phase and gas phase pollutant treatment because of the advantages of large forbidden bandwidth, strong redox capability, high photocatalytic activity and the like. But the wide forbidden band characteristic reduces the utilization rate of sunlight, so that the application of the solar cell is limited. Researches in recent years find that the visible light catalytic performance of the BiOCl can be improved by adjusting and controlling the BiOCl energy band structure through metal ion doping.
Manganese-, tungsten-, cobalt-and iron-doped BiOCl was prepared and its visible photocatalytic activity was studied, as by hydrolysis [ Applied Surface Science 258 (2011) 247-253], solvothermal [ Phys.chem.chem.chem.Phys.16 (2014) 21349-21355], hydrothermal [ Applied Catalysis B: environmental 221 (2018) 320-328] and combustion [ Separation and Purification Technology 162 (2016) 114-119], respectively. Other BiOCl doped with alkali metal and rare earth metal (Chinese patent No. CN 107597150A) are also widely studied. Calculation of Jingfa Li and the like shows that indium-doped BiOCl can enable the conduction band potential to be more negative [ Chemical Physics Letter 705 (2018) 31-37], the conduction band electron reduction efficiency is improved, but the forbidden band width is increased, the visible light efficiency is not favorably improved, and therefore no report is made on the indium-doped BiOCl visible light catalyst.
Disclosure of Invention
In order to solve the problems, the invention adopts a solvothermal method for preparing In by using a mixed system of glycol and water 3+ Exposing BiOCl nanosheets by doping (001) crystal faces, and obtaining In by ultraviolet irradiation at room temperature + And doping the oxygen-containing vacancy BiOCl nanosheet visible-light photocatalyst with an exposed (001) crystal face. In prepared by the invention + The oxygen vacancy BiOCl nanosheet with the exposed (001) crystal face can efficiently degrade high-concentration sodium pentachlorophenate serving as pesticide under visible light, after visible light irradiation for half an hour, the sodium pentachlorophenate with the concentration of 20 mg/L can be almost completely degraded, and the degradation rate respectively reaches 6.8 times and In times of that of the oxygen vacancy BiOCl nanosheet with the exposed (001) crystal face not doped with indium 3+ The (001) doped crystal face exposes 27.4 times of the BiOCl nanosheet. The method has the advantages of simple process, low cost, environmental friendliness and convenience for further expanded production.
In the present invention for achieving the above object + The preparation method of the (001) crystal face-doped oxygen-containing vacancy BiOCl nanosheet adopts the following technical means, and comprises the following steps:
In + a preparation method of a (001) crystal face-doped oxygen-containing vacancy BiOCl nanosheet,
1) Adding bismuth nitrate, indium nitrate and potassium chloride into a mixed solution of water and ethylene glycol, and forming a suspension under magnetic stirring, wherein the volume ratio of the water to the ethylene glycol is 1: 8-1: 3;
2) Placing the suspension obtained in the step 1) in a polytetrafluoroethylene reaction kettle at 160 DEG C o C～180 o Standing for 10-30 hours in the atmosphere of C to form a precipitate;
3) Washing and drying the precipitate obtained In the step 2) to obtain In 3+ Doping a (001) crystal face to expose BiOCl nanosheets;
4) Subjecting the sample obtained In the step 3) to ultraviolet irradiation to obtain In + The (001) doped crystal face exposes the BiOCl nanosheet containing oxygen vacancies.
In as the present invention + Further improvement of the (001) doped crystal face exposed oxygen-containing vacancy BiOCl nanosheet: the mass ratio of indium element to bismuth element in the step 1) is 1:100 to 5:100, total volume 40 mL, bismuth nitrate and indium nitrateThe sum of the amounts of the substances is equal to the amount of the substance of potassium chloride.
In as the present invention + Further improvement of the (001) doped crystal face exposed oxygen-containing vacancy BiOCl nanosheet: the ultraviolet irradiation in the step 4) is carried out at room temperature, the sample is within 10cm from the light source and is continuously irradiated for 1-4 hours under the ultraviolet light emitted by a 300-watt mercury lamp, the ultraviolet light wavelength range of the mercury lamp is 350-450 nm, and the wavelength peak value is 365 nm.
In + The (001) -doped crystal face-exposed oxygen-containing vacancy BiOCl nanosheet is characterized in that: in (In) 3+ Forming In by exposing BiOCl nanosheet with (001) doped crystal face through ultraviolet illumination + The (001) doped crystal face exposes BiOCl nano-sheets containing oxygen vacancies, the size is less than 200 nm, and the thickness is 15-25 nm.
Said In + And (001) crystal face-doped BiOCl nanosheets with exposed oxygen-containing vacancies are used as visible light photocatalysts.
Advantageous effects
Compared with the prior art, the invention has the following beneficial effects:
first, in prepared by the present invention + The (001) doped crystal face exposes the oxygen-containing vacancy BiOCl nanosheet, the size of the oxygen-containing vacancy BiOCl nanosheet is less than 200 nm, the thickness of the oxygen-containing vacancy BiOCl nanosheet is 15-25 nm, and the oxygen-containing vacancy BiOCl nanosheet is about half of the size of the P-doped BiOCl nanosheet prepared by a similar method. The specific surface area is increased, and the photocatalytic activity is favorably improved. In prepared by the invention + Indium element In the (001) crystal face-doped oxygen vacancy-containing BiOCl nanosheet replaces bismuth element In crystal lattice, 20 mg/L sodium pentachlorophenate can be almost completely degraded In half an hour under visible light, the degradation rate reaches 6.8 times that of the (001) crystal face-doped non-indium crystal face-exposed oxygen vacancy-containing BiOCl nanosheet, and is In 3+ The (001) doped crystal face exposes 27.4 times of the BiOCl nanosheet.
Second, in according to the present invention + In the preparation of the (001) crystal face-doped oxygen-containing vacancy BiOCl nanosheet, the volume ratio of water to ethylene glycol is set to be 1: 8-1: 3, a large number of experiments show that BiOCl graded spherical structures are easy to generate if the volume ratio of ethylene glycol is higher than the range, and the size of BiOCl slices obtained below the range is obviously increased, so that the specific surface area of a sample is reduced, and the photocatalysis is promotedAnd (4) activity. In addition, the presence of ethylene glycol also avoids In (OH) 3 And the generation of the precipitate ensures that the indium is doped into the BiOCl in an ionic form. Meanwhile, when the quantity ratio of the indium element to the bismuth element is higher than 5: when 100, impurities are easily generated.
Third, in prepared by the present invention + The (001) doped crystal face exposes the oxygen-containing vacancy BiOCl nanosheet, so that the visible light photocatalytic activity of indium-doped BiOCl is realized, the efficiency of degrading high-concentration water pollutants such as sodium pentachlorophenate serving as an insecticide is greatly improved, and a new photocatalytic material is provided for environmental water pollution treatment.
Fourthly, the ultraviolet irradiation for 1 to 4 hours In the invention leads BiOCl to generate oxygen vacancy, simultaneously excites BiOCl intrinsic energy band and promotes the generation of photo-generated electrons, thus leading In to be 3+ Reduction to In + ，In + The existence of the metal oxide can further improve the separation efficiency of electrons and holes in the visible light catalytic reaction and improve the visible light catalytic activity.
Fifthly, the whole process is simple and easy to control, low in energy consumption, high in yield and low in cost, and meets the actual production requirement.
Sixthly, the invention has the advantages of cheap and easily obtained raw materials, mild reaction conditions, low energy consumption, low requirement on equipment and In + The oxygen vacancy coexists in the (001) crystal face exposed BiOCl nanosheet, the separation efficiency of electron holes under visible light is greatly improved, high-concentration water pollutants can be rapidly degraded, and the method has a good application prospect.
Drawings
FIG. 1 shows In prepared In example 2 3+ BiOCl nanosheet exposed by doping (001) crystal face, in prepared In example 4 + XRD diffractograms of (001) crystal face-doped exposed oxygen-containing vacancy BiOCl nanosheets and (001) crystal face-exposed oxygen-containing vacancy BiOCl nanosheets samples prepared in example 1.
FIG. 2 shows XPS survey spectra and high resolution spectra of In 3d of samples obtained In examples 2 and 4.
FIG. 3 is a TEM, SAED and HRTEM image of the samples obtained in example 2 (3 a, 3b, 3 c) and example 4 (3 d, 3e, 3 f).
FIG. 4 is an EPR spectrum of the sample obtained in example 4.
FIG. 5 shows In prepared In example 2 3+ BiOCl nanosheet with (001) -doped crystal face exposed and In prepared In example 4 + And (001) doped crystal face exposes an ultraviolet visible absorption spectrum diagram of the oxygen-containing vacancy BiOCl nanosheet.
FIG. 6 shows In obtained In example 4 + Doping of (001) Crystal face exposing oxygen vacancy containing BiOCl nanoplates, in prepared In example 2 3+ A comparative graph of the effect of (001) -surface-doped exposed BiOCl nanosheet and the effect of the (001) -surface-exposed oxygen-containing vacancy BiOCl nanosheet prepared in example 1 on degrading pesticide sodium pentachlorophenate under visible light is shown.
FIG. 7 shows In prepared In examples 3,4,5 and 6 + And (001) crystal face-doped exposed oxygen-containing vacancy BiOCl nanosheet sample photocatalytic activity comparison graph.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples, which are provided for the purpose of explaining the technical solutions of the present invention in detail.
The present invention discloses In + BiOCl nanosheet with exposed (001) crystal face, preparation method thereof and In + The (001) crystal face-doped BiOCl nanosheet is used as a photocatalyst to efficiently degrade high-concentration water pollutants such as sodium pentachlorophenate serving as an insecticide, so that a novel photocatalytic material is provided for environmental water pollution treatment.
In the application of the invention, biOCl nanosheets and In with exposed oxygen-containing vacancies In (001) crystal faces are prepared In examples 1 and 2 respectively 3+ Doping (001) crystal face exposing BiOCl nano-sheet as In to be protected by the patent application + An experimental control group with (001) doped crystal faces exposing BiOCl nanosheets was used.
Example 1
The preparation method for preparing the (001) crystal face exposed oxygen vacancy-containing BiOCl nanosheet in this embodiment is that bismuth nitrate and potassium chloride (wherein the mass ratio of the bismuth nitrate to the potassium chloride is 1) are added into a mixed solution of water and ethylene glycol (the volume ratio of the ethylene glycol to the water is 1; at 160 o Standing for 20 hours in the atmosphere of C to form a precipitate, drying the obtained precipitate to obtain the (001) crystal face exposed BiOCl nanosheet, and then irradiating for 2 hours under ultraviolet light (300W mercury lamp) to obtain the (001) crystal face exposed oxygen-containing vacancy BiOCl nanosheet.
Example 2
In this example + The preparation method of the (001) crystal face-doped oxygen-containing vacancy BiOCl nanosheet comprises the steps of adding bismuth nitrate, indium nitrate and potassium chloride (wherein the mass ratio of the bismuth nitrate to the indium nitrate is 1 to 100) into a mixed solution of water and ethylene glycol (the volume ratio of the ethylene glycol to the water is 1; at 160 o Standing for 20 hr In C atmosphere to form precipitate, and oven drying the precipitate to obtain In 3+ And (001) crystal face doping exposes the BiOCl nanosheet.
Example 3
In this example + The preparation method of the (001) doped face-exposed oxygen-containing vacancy BiOCl nanosheet comprises the steps of adding bismuth nitrate, indium nitrate and potassium chloride (wherein the mass ratio of the bismuth nitrate to the indium nitrate is 1:100, and the sum of the mass of the bismuth nitrate and the indium nitrate is equal to the mass of the potassium chloride) into a mixed solution of water and glycol (the volume ratio of glycol to water is 1; at 160 o Standing In C atmosphere for 20 hr to form precipitate, and oven drying the precipitate to obtain In 3+ Exposing the BiOCl nano-sheet by doping (001) crystal face, and then irradiating for 1 hour under ultraviolet light (300W mercury lamp) to obtain In + Specifically, the sample ultraviolet irradiation process is carried out at room temperature, the sample is within 10cm from a light source, and the sample is continuously irradiated for 1 hour under the ultraviolet light source emitted by a 300 watt mercury lamp, so as to obtain In + The (001) doped crystal face exposes the oxygen-containing vacancy BiOCl nanosheet.
Example 4
In this example + The preparation method of the (001) -crystal-face-doped oxygen-containing vacancy BiOCl nanosheet comprises the steps of adding bismuth nitrate, indium nitrate and potassium chloride(wherein the ratio of the amount of bismuth nitrate to the amount of indium nitrate is 1; at 160 o Standing for 20 hr In C atmosphere to form precipitate, and oven drying the precipitate to obtain In 3+ Exposing the BiOCl nano-sheet by doping (001) crystal face, then exposing the sample to an ultraviolet light source within 10cm at room temperature, and continuously irradiating for 2 hours under ultraviolet light (300W mercury lamp) to obtain In + The (001) doped crystal face exposes the BiOCl nanosheet containing oxygen vacancies.
Example 5
In this example + The preparation method of the (001) crystal face-doped oxygen-containing vacancy BiOCl nanosheet comprises the steps of adding bismuth nitrate, indium nitrate and potassium chloride (wherein the mass ratio of the bismuth nitrate to the indium nitrate is 5:100, and the sum of the mass of the bismuth nitrate and the mass of the indium nitrate is equal to the mass of the potassium chloride) into a mixed solution of water and ethylene glycol (the volume ratio of the ethylene glycol to the water is 1; at 160 o Standing for 20 hr In C atmosphere to form precipitate, and oven drying the precipitate to obtain In 3+ Exposing a (001) -doped crystal face to a BiOCl nanosheet, then exposing a sample to an ultraviolet light source within 10cm at room temperature, and illuminating for 4 hours under ultraviolet light (300W mercury lamp) to obtain In + And (001) crystal face doping exposes the BiOCl nanosheet.
Example 6
In this example + The preparation method of the (001) crystal face-doped oxygen-containing vacancy BiOCl nanosheet comprises the steps of adding bismuth nitrate, indium nitrate and potassium chloride (wherein the mass ratio of the bismuth nitrate to the indium nitrate is 5:100, and the sum of the mass of the bismuth nitrate and the mass of the indium nitrate is equal to the mass of the potassium chloride) into a mixed solution of water and ethylene glycol (the volume ratio of the ethylene glycol to the water is 1; at 180 o Standing for 20 hr In C atmosphere to form precipitate, and oven drying the precipitate to obtain In 3+ Exposing the BiOCl nano-sheet by doping (001) crystal face, then exposing the sample to an ultraviolet light source within 10cm at room temperature, and irradiating for 4 hours under ultraviolet light (300W mercury lamp) to obtain In + And (001) crystal face doping exposes the BiOCl nanosheet.
The invention proceeds with In the examples described above + Preparing a (001) crystal face-doped exposed oxygen-containing vacancy BiOCl nanosheet and analyzing data:
as shown in figure 1, when XRD diffraction analysis is carried out on various BiOCl nanosheet samples, the data are compared with a standard card, and the diffraction peaks of the two samples in the figure are consistent with a standard spectrum of BiOCl (JCPDS No: 6-249), and No other impurity phase exists. Doping with In XRD pattern 3+ And In + The diffraction peak of the BiOCl sample is shifted to a high-angle direction, and the fact that In replaces Bi to enter a BiOCl crystal lattice is proved.
The existence of indium element can be seen from the full spectrum of FIG. 2, and In can be found by comparing the high resolution spectrum diagram of In 3d + In 3d binding energy ratio In (001) -crystal-face-doped exposed oxygen-containing vacancy BiOCl nanosheet 3+ About 0.4 electron ford In the BiOCl nanosheet with the exposed (001) crystal face proves that the indium element In the sample prepared In example 4 is In + The state of (2) exists.
In FIG. 3, in produced can be seen from TEM 3+ Doping (001) crystal face exposing BiOCl nanosheet and In + The sizes of the (001) doped crystal face exposed oxygen-containing vacancy BiOCl nano-chips are less than 200 nm, and the thicknesses of the nano-chips are about 20 nm. From HRTEM and SAED pictures, the upper and lower faces of the nanosheets prepared in examples 2 and 4 are (001) crystal faces.
In after UV irradiation was confirmed from the EPR spectrum of FIG. 4 + The (001) doped crystal face exposes the presence of oxygen vacancies in the oxygen-vacancy BiOCl nanoplates.
From the UV-VIS absorption spectrum of FIG. 5, in 3+ Compared with the BiOCl nano-sheet with the exposed (001) crystal face although In + The energy band of the (001) doped crystal face exposed oxygen-containing vacancy BiOCl nanosheet is not obviously changed, but the impurity level absorption phenomenon is strong in the visible light range.
In FIG. 6 byThe effect comparison graph of the BiOCl nanosheet for degrading the sodium pentachlorophenate serving as the insecticide under the visible light shows that the activity of the photocatalyst is tested by degrading the sodium pentachlorophenate serving as the insecticide under the visible light, wherein a 500W xenon lamp is used as a light source, a filter is added, and light with the wavelength of less than 420 nm is filtered out, so that the visible light is obtained. The dosage of the catalyst is 0.05 g, the concentration of the sodium pentachlorophenate solution is 20 mg/L, and the volume is 50 mL. As can be seen from the figure, in example 4 was observed after half an hour of irradiation with visible light + The (001) surface doped and oxygen vacancy-containing BiOCl nanosheet can almost completely degrade sodium pentachlorophenate, and the degradation rate of the sodium pentachlorophenate is 6.8 times that of the (001) surface exposed and oxygen vacancy-containing BiOCl nanosheet In example 1 and is In example 2 3+ Doping the (001) crystal face exposes 27.4 times the BiOCl nanoplates.
For In prepared In examples 3,4,5 and 6 + The photocatalytic activity of the sample with the (001) doped crystal surface exposed with the oxygen-containing vacancy BiOCl nanosheet is compared (as shown in FIG. 7), and it can be seen that the photocatalytic activity of the sample prepared in example 3 is the weakest after being irradiated by ultraviolet light for 1 hour, the efficiency of photocatalytic degradation of pesticide sodium pentachlorophenate in the sample with visible light after being irradiated by ultraviolet light for more than 2 hours is equivalent, and the changes of the three conditions have no obvious influence on the catalytic activity within the range of the proportion of ethylene glycol to water, the range of the proportion of bismuth element to indium element and the temperature range of the dissolution heat reaction.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention.
Claims (5)
1.In + Doping (001) crystal face exposing oxygen-containing vacancy BiOThe preparation method of the Cl nanosheet is characterized by comprising the following steps:
adding bismuth nitrate, indium nitrate and potassium chloride into a mixed solution of water and ethylene glycol, and forming a suspension under magnetic stirring, wherein the volume ratio of the water to the ethylene glycol is 1: 8-1: 3;
placing the suspension obtained in the step 1) in a polytetrafluoroethylene reaction kettle at 160 DEG C o C～180 o Standing for 10-30 hours in the atmosphere of C to form a precipitate;
washing and drying the precipitate obtained In the step 2) to obtain In 3+ Doping a (001) crystal face to expose a BiOCl nanosheet sample;
subjecting the sample obtained In the step 3) to ultraviolet irradiation to obtain In + The (001) doped crystal face exposes the BiOCl nanosheet containing oxygen vacancies.
2. In according to claim 1 + The preparation method of the (001) -crystal-face-doped oxygen-containing vacancy BiOCl nanosheet is characterized by comprising the following steps of: the total volume of the suspension in the step 1) is 40 mL, the sum of the amounts of bismuth nitrate and indium nitrate is equal to the amount of potassium chloride, and the amount ratio of indium element to bismuth element is 1:100 to 5:100.
3. in according to claim 1 + The preparation method of the (001) -crystal-face-doped oxygen-containing vacancy BiOCl nanosheet is characterized by comprising the following steps of: and 4) carrying out ultraviolet illumination at room temperature in the step 4), wherein the sample is within 10cm from the light source and is continuously illuminated for 1-4 hours under the ultraviolet light emitted by a 300-watt mercury lamp, the wavelength range of the ultraviolet light of the mercury lamp is 350-450 nm, and the peak value of the wavelength is 365 nm.
4. An In as claimed In any one of claims 1 to 3 + The (001) -doped crystal face-exposed oxygen-containing vacancy BiOCl nanosheet is characterized in that: in (In) 3+ Forming In by exposing BiOCl nano-sheet with (001) doped crystal face through ultraviolet irradiation + The (001) doped crystal face exposes BiOCl nano-sheets containing oxygen vacancies, the size of the sheet is less than 200 nm, and the thickness is 15-25 nm.
5. In according to claim 4 + The application of the (001) -doped crystal face exposed oxygen-containing vacancy BiOCl nanosheet is characterized in that: said In + And (001) crystal face-doped BiOCl nanosheets with exposed oxygen-containing vacancies are used as visible-light catalysts.
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| CN104069876A (en) * | 2014-06-24 | 2014-10-01 | 华中师范大学 | Ag-BiOCl compound photocatalyst prepared by depositing nanometer silver on [001] crystal face of BiOCl nanometer sheet and method |
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