CN115636440B - In+ doped (001) crystal face exposed oxygen-containing vacancy BiOCl nano sheet and preparation method thereof - Google Patents
In+ doped (001) crystal face exposed oxygen-containing vacancy BiOCl nano sheet 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 95
- 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 52
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 52
- 239000001301 oxygen Substances 0.000 title claims abstract description 52
- 239000002135 nanosheet Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 57
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 32
- 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 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 18
- 229910052738 indium Inorganic materials 0.000 claims abstract description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 16
- 239000001103 potassium chloride Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- -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
- 239000002055 nanoplate Substances 0.000 abstract description 11
- 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 11
- 238000000034 method Methods 0.000 abstract description 7
- 239000000575 pesticide Substances 0.000 abstract description 6
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000002064 nanoplatelet Substances 0.000 description 25
- 230000001699 photocatalysis Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000012535 impurity 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 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
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 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
- 239000000243 solution Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
Classifications
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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
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Abstract
The invention discloses an In + A (001) crystal face doped oxygen-containing vacancy BiOCl nano-sheet visible light photocatalyst and a preparation method thereof. Bismuth nitrate, indium nitrate and potassium chloride are used as precursors (the mass ratio of indium element to bismuth element is 1:100-5:100, and the mixed solution of ethylene glycol and water with the volume ratio of 1:8-1:3 is used as a solvent, and the mixed solution is prepared by mixing at least one of the following components o C～180 o C reacts for 10 to 30 hours to obtain In 3+ Doping (001) crystal face to expose BiOCl nano-sheet, and obtaining In after ultraviolet irradiation of the obtained sample for 1-4 hours + The doped (001) crystal face exposes oxygen-containing vacancy BiOCl nano-plate, the size is smaller than 200nm, and the thickness is 15-25 nm. The (001) crystal face prepared by the method of the invention exposes In the BiOCl nano-sheet + And the indium replaces the bismuth element and can efficiently degrade the pesticide sodium pentachlorophenate under visible light. The invention has simple process, low cost, environment-friendly property and high yield, is suitable for large-scale production, meets the actual production requirement, and has great application potential.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic materials, and In particular relates to an In + Doped (001) crystal face exposure oxygen-containing vacancy BiOCl nano-sheet and a preparation method thereof.
Background
BiOCl has a unique layered structure and is applied to the field of liquid-phase and gas-phase pollutant treatment due to the advantages of large forbidden bandwidth, strong redox capacity, high photocatalytic activity and the like. But its wide forbidden band characteristic reduces the utilization of sunlight, making its application limited. In recent years, research shows that the doping of metal ions can regulate and control the BiOCl energy band structure to improve the visible light catalytic performance.
Manganese, tungsten, cobalt and iron doped BiOCl were prepared and studied for visible light catalytic activity as by hydrolysis [ Applied Surface Science (2011) 247-253], solvothermal [ Phys.chem.chem.Phys.16 (2014) 21349-21355], hydrothermal [ AppliedCatalysis B: environmental 221 (2018) 320-328] and combustion [ Separationand Purification Technology (2016) 114-119], respectively. Other such as alkali and rare earth doped BiOCl [ Chinese patent invention CN107597150A ] are also widely studied. The calculation of Jinfa Li and the like shows that the indium doped BiOCl can lead the conduction band potential to be more negative [ Chemical Physics Letter 705 (2018) 31-37], thereby improving the conduction band electron reduction efficiency, but the energy gap is increased, which is unfavorable for improving the visible light efficiency, so the indium doped BiOCl visible light catalyst has not been reported so far.
Disclosure of Invention
In order to solve the problems, the invention adopts the solvent-thermal method of the ethylene glycol and water mixed system to prepare In 3+ Doping (001) crystal face to expose BiOCl nano-sheet, and making UV irradiation at room temperature to obtain In + Doping (001) crystal face exposure oxygen-containing vacancy BiOCl nano-sheet visible light photocatalyst. In prepared by the invention + The oxygen-containing vacancy BiOCl nano-sheet exposed by the doped (001) crystal face can efficiently degrade high-concentration insecticide sodium pentachlorophenate under visible light, and can be used for preparing 2 after half an hour of visible light irradiationSodium pentachlorophenate of 0 mg/L is almost completely degraded, and the degradation rate is 6.8 times of that of the (001) crystal face exposure oxygen-containing vacancy BiOCl nano-sheet of undoped indium and In respectively 3+ The doped (001) crystal plane exposes 27.4 times of the BiOCl nanoplatelets. The invention has simple process, low cost, environmental protection and convenient further expansion production.
To achieve the above object, in according to the present invention + The preparation method of the (001) crystal face doped oxygen-containing vacancy BiOCl nano-sheet adopts the following technical means, and comprises the following steps:
In + a preparation method of a doped (001) crystal face exposed oxygen-containing vacancy BiOCl nano-sheet,
1) Bismuth nitrate, indium nitrate and potassium chloride are added into a mixed solution of water and glycol, and a suspension is formed under magnetic stirring, wherein the volume ratio of the water to the glycol is 1: 8-1: 3, a step of;
2) Placing the suspension obtained in the step 1) into a polytetrafluoroethylene reaction kettle, and at 160 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 (001) crystal faces to expose the BiOCl nano-sheets;
4) Obtaining In by ultraviolet irradiation of the sample obtained In the step 3) + The doped (001) crystal plane exposes the oxygen-containing vacancy BiOCl nanoplatelets.
In as the present invention + Further improvement of doping (001) crystal face exposed oxygen-containing vacancy BiOCl nanoplatelets: the mass ratio of the indium element to the bismuth element in the step 1) is 1: 100-5: 100, total volume 40mL, the sum of the amounts of bismuth nitrate and indium nitrate material being equal to the amount of potassium chloride material.
In as the present invention + Further improvement of doping (001) crystal face exposed oxygen-containing vacancy BiOCl nanoplatelets: the ultraviolet irradiation in the step 4) is carried out at room temperature, the sample is within a distance of within a light source 10cm and continuously irradiates for 1-4 hours under the ultraviolet light emitted by a 300W mercury lamp, the ultraviolet light wavelength range of the mercury lamp is 350 nm-450 nm, and the wavelength peak value is 365nm.
In + Doping (001) the crystal face exposure containsThe oxygen vacancy BiOCl nano-sheet is characterized in that: in (In) 3+ Doping (001) crystal face exposure BiOCl nano-sheet to form In by ultraviolet irradiation + The BiOCl nano-plate with the doped (001) crystal face exposing oxygen-containing vacancies has the size smaller than 200nm and the thickness of 15-25 nm.
The In is + The (001) crystal face-doped oxygen-containing vacancy BiOCl nano-sheet is used as a visible light photocatalyst.
Advantageous effects
Compared with the prior art, the invention has the following beneficial effects:
first, in prepared according to the present invention + The doped (001) crystal face exposes the oxygen-containing vacancy BiOCl nano-plate, the size is less than 200nm, the thickness is 15-25 nm, and the size is about half of that of the P doped BiOCl nano-plate prepared by a similar method. The specific surface area is increased, and the photocatalytic activity is improved. In prepared by the invention + The indium element In the (001) crystal face-exposed oxygen-containing vacancy BiOCl nano-sheet replaces bismuth element In crystal lattice, and can almost completely degrade 20 mg/L sodium pentachlorophenate In half an hour under visible light, the degradation rate is 6.8 times of that of the (001) crystal face-exposed oxygen-containing vacancy BiOCl nano-sheet without doped indium, and the degradation rate is In 3+ The doped (001) crystal plane exposes 27.4 times of the BiOCl nanoplatelets.
Second, in according to the present invention + In the preparation of the (001) crystal face doped oxygen-containing vacancy BiOCl nano-sheet, the volume ratio of water to glycol is set to be 1: 8-1: 3, a large number of experiments prove that if the volume ratio of the ethylene glycol is higher than that of the range, the BiOCl graded spherical structure is easy to generate, and the size of the BiOCl tablet obtained below the range is obviously increased, so that the specific surface area and the photocatalytic activity of the sample are reduced. In addition, the presence of ethylene glycol also avoids In (OH) 3 The formation of a precipitate ensures that indium is doped in the form of ions into BiOCl. Meanwhile, when the mass ratio of the indium element to the bismuth element substance is higher than 5: impurities are easily generated at 100.
Third, in prepared according to the present invention + The (001) crystal face doped BiOCl nano-sheet with oxygen-containing vacancy is exposed, the visible light photocatalytic activity of indium doped BiOCl is realized, the efficiency of degrading high-concentration water pollutants such as pesticide sodium pentachlorophenate is greatly improved,provides a new photocatalysis material for environmental water pollution control.
Fourth, the ultraviolet irradiation of the invention for 1-4 hours causes BiOCl to generate oxygen vacancies, and simultaneously excites BiOCl intrinsic energy band to promote the generation of photo-generated electrons, which causes In 3+ Reduction to In + ，In + The existence of the catalyst further improves the separation efficiency of electrons and holes in the visible light catalytic reaction, and improves the visible light catalytic activity.
Fifth, the whole process is simple and easy to control, consumes less energy, has high yield and low cost, and meets the actual production requirement.
Sixthly, the invention has the advantages of cheap and easily obtained raw materials, mild reaction condition, less energy consumption, low requirement on equipment and In + The oxygen vacancies coexist in the (001) crystal face exposed BiOCl nano-sheet, so that the separation efficiency of electron holes under visible light is greatly improved, high-concentration water pollutants can be rapidly degraded, and the method has good application prospects.
Drawings
FIG. 1 is an In prepared In example 2 3+ Doping (001) Crystal face exposed BiOCl nanoplatelets, in prepared In example 4 + XRD diffractograms of the (001) crystal face-exposed oxygen-containing vacancy BiOCl nanoplatelets and the (001) crystal face-exposed oxygen-containing vacancy BiOCl nanoplatelet samples prepared in example 1.
Fig. 2 is an XPS full spectrum and a high resolution energy spectrum of In 3d of the samples obtained In example 2 and example 4.
Fig. 3 is TEM, SAED and HRTEM images of 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 is an In prepared In example 2 3+ Doping (001) Crystal face exposed BiOCl nanoplatelets and In prepared In example 4 + Ultraviolet visible absorption spectrum of the doped (001) crystal face exposed oxygen-containing vacancy BiOCl nano-sheet.
FIG. 6 is an In obtained In example 4 + Doping (001) Crystal face-exposed oxygen-containing vacancy BiOCl nanoplatelets, in prepared In example 2 3+ Doping of (001) Crystal face-exposed BiOCl nanoplates and (001) Crystal face-exposed prepared in example 1The effect comparison chart of the oxygen-containing vacancy BiOCl nano-sheet on degrading pesticide sodium pentachlorophenate under visible light.
FIG. 7 shows In prepared In examples 3,4,5 and 6 + Photo-catalytic activity comparison of the doped (001) crystal plane exposed oxygen-containing vacancy BiOCl nanoplatelet sample.
Detailed Description
The present invention is further described below with reference to the accompanying drawings and specific examples, which provide detailed embodiments on the premise of the technical scheme of the present invention.
The invention discloses In + Doped (001) crystal face exposed BiOCl nano-sheet, preparation method thereof and In + The doped (001) crystal face exposed BiOCl nano-plate is used as a photocatalyst to efficiently degrade high-concentration water pollutants such as pesticide sodium pentachlorophenate, so that a novel photocatalytic material is provided for environmental water pollution control.
In the present application, example 1 and example 2 were prepared respectively (001) crystal face-exposed oxygen-containing vacancy BiOCl nanoplatelets and In 3+ Doping (001) crystal face to expose BiOCl nano-plate as In to be protected by the patent application of the invention + An experimental control group doped with (001) crystal face-exposed BiOCl nanoplates was used.
Example 1
The preparation method of the (001) crystal face-exposed oxygen-containing vacancy BiOCl nano-sheet in the embodiment comprises the steps of adding bismuth nitrate and potassium chloride (wherein the quantity ratio of bismuth nitrate to potassium chloride is 1:1) into a mixed solution of water and ethylene glycol (the volume ratio of ethylene glycol to water is 1:8), and forming a suspension with magnetic stirring, wherein the volume of the suspension is 40 mL; at 160 o And (3) standing for 20 hours in the atmosphere of C to form a precipitate, drying the obtained precipitate to obtain the (001) crystal face exposure BiOCl nano-sheet, and then irradiating for 2 hours under ultraviolet light (300 watt mercury lamp) to obtain the (001) crystal face exposure oxygen-containing vacancy BiOCl nano-sheet.
Example 2
In the present embodiment + The preparation method of the BiOCl nano-sheet with the oxygen-containing vacancy exposed by doping (001) crystal face comprises the steps of adding bismuth nitrate, indium nitrate and potassium chloride (wherein bismuth nitrate and nitrateThe mass ratio of the indium acid substance is 1:100 Adding the mixture of water and glycol (the volume ratio of glycol to water is 1: 8) Forming a suspension with magnetic stirring, wherein the volume of the suspension is 40 mL; at 160 o Standing In atmosphere of C for 20 hr to form precipitate, and oven drying the precipitate to obtain In 3+ Doping (001) crystal planes exposes the BiOCl nanoplatelets.
Example 3
In the present embodiment + The preparation method of the bismuth nitrate, indium nitrate and potassium chloride (wherein the quantity ratio of bismuth nitrate to indium nitrate is 1:100, the sum of the quantity of bismuth nitrate and indium nitrate is equal to that of potassium chloride) added into a mixed solution of water and glycol (the volume ratio of glycol to water is 1:8), and a suspension is formed under magnetic stirring, and the volume of the suspension is 40 mL; at 160 o Standing In atmosphere of C for 20 hr to form precipitate, and oven drying the precipitate to obtain In 3+ Doping (001) crystal face to expose BiOCl nano-plate, and then irradiating under ultraviolet light (300W Hg lamp) for 1 hr to obtain In + Doping (001) crystal face to expose oxygen-containing vacancy BiOCl nano-sheet, specifically, performing sample ultraviolet irradiation at room temperature, keeping the sample within 10cm from the light source, and continuously irradiating under ultraviolet light source of 300W mercury lamp for 1 hr to obtain In + The doped (001) crystal plane exposes the oxygen-containing vacancy BiOCl nanoplatelets.
Example 4
In the present embodiment + The preparation method of the doped (001) crystal face-exposed oxygen-containing vacancy BiOCl nano-sheet comprises the steps of adding bismuth nitrate, indium nitrate and potassium chloride (wherein the quantity ratio of bismuth nitrate to indium nitrate is 1:100, the sum of the quantity of bismuth nitrate and indium nitrate is equal to that of potassium chloride), into a mixed solution of water and ethylene glycol (the volume ratio of ethylene glycol to water is 1:8), and forming a suspension under magnetic stirring, wherein the volume of the suspension is 40 mL; at 160 o Standing In atmosphere of C for 20 hr to form precipitate, and oven drying the precipitate to obtain In 3+ Doping (001) crystal face to expose BiOCl nano-sheet, then exposing sample at room temperatureExposing to ultraviolet light source within 10cm, and continuously irradiating with ultraviolet light (300W Hg lamp) for 2 hr to obtain In + The doped (001) crystal plane exposes the oxygen-containing vacancy BiOCl nanoplatelets.
Example 5
In the present embodiment + The preparation method of the doped (001) crystal face-exposed oxygen-containing vacancy BiOCl nano-sheet comprises the steps of adding bismuth nitrate, indium nitrate and potassium chloride (wherein the quantity ratio of bismuth nitrate to indium nitrate substances is 5:100, and the sum of the quantity of bismuth nitrate and indium nitrate substances is equal to that of potassium chloride substances) into a mixed solution of water and ethylene glycol (the volume ratio of ethylene glycol to water is 1:5), and forming a suspension under magnetic stirring, wherein the volume of the suspension is 40 mL; at 160 o Standing In atmosphere of C for 20 hr to form precipitate, and oven drying the precipitate to obtain In 3+ Doping (001) crystal face to expose BiOCl nano-plate, then exposing sample into ultraviolet light source 10cm at room temperature, and irradiating under ultraviolet light (300W Hg lamp) for 4 hours to obtain In + Doping (001) crystal planes exposes the BiOCl nanoplatelets.
Example 6
In the present embodiment + The preparation method of the doped (001) crystal face-exposed oxygen-containing vacancy BiOCl nano-sheet comprises the steps of adding bismuth nitrate, indium nitrate and potassium chloride (wherein the quantity ratio of bismuth nitrate to indium nitrate substances is 5:100, the sum of the quantity of bismuth nitrate and indium nitrate substances is equal to that of potassium chloride substances) into a mixed solution of water and ethylene glycol (the volume ratio of ethylene glycol to water is 1:3), and forming a suspension under magnetic stirring, wherein the volume of the suspension is 40 mL; at 180 o Standing In atmosphere of C for 20 hr to form precipitate, and oven drying the precipitate to obtain In 3+ Doping (001) crystal face to expose BiOCl nanometer sheet, exposing sample into ultraviolet light source 10cm at room temperature, and irradiating under ultraviolet light (300W Hg lamp) for 4 hr to obtain In + Doping (001) crystal planes exposes the BiOCl nanoplatelets.
In was carried out In the above examples of the invention + Preparation of doped (001) crystal face-exposed oxygen-containing vacancy BiOCl nanoplatelets and data analysis:
each BiOCl nanoplatelet sample was subjected to as in FIG. 1XRD diffraction analysis shows that the diffraction peaks of the two samples in the graph are identical with the standard spectrum of BiOCl (JCPLDS No. 6-249) and No other impurity phase exists through the comparison of the data and the standard card. Doping In XRD patterns 3+ And In + The diffraction peak of the BiOCl sample moves to a high angle direction, and the fact that In replaces Bi and enters the BiOCl lattice is proved.
The presence of indium element can be seen from the full spectrum of FIG. 2, and In can be found by comparing the high-resolution energy spectrum of In 3d + In 3d binding energy ratio In of doped (001) crystal face exposed oxygen-containing vacancy BiOCl nano-sheet 3+ The doping (001) crystal face exposed BiOCl nano-sheet has about 0.4 electron Ford lower, which proves that indium element In the sample prepared In example 4 is expressed as In + Is present.
In FIG. 3, it can be seen from TEM that In was prepared 3+ Doping (001) crystal face to expose BiOCl nano-plate and In + The dimension of the doped (001) crystal face exposed oxygen-containing vacancy BiOCl nano-sheet is smaller than 200nm, and the thickness is about 20 nm. From the HRTEM and SAED pictures, it can be seen that the upper and lower surfaces of the nanoplatelets prepared in example 2 and example 4 are both (001) crystal planes.
In after UV irradiation was confirmed from the EPR spectrum of FIG. 4 + The doped (001) crystal plane exposes the presence of oxygen vacancies in the oxygen-containing vacancy BiOCl nanoplatelets.
As can be seen from the ultraviolet-visible absorption spectrum of FIG. 5, it is preferable to obtain a spectrum with In 3+ Doped (001) crystal plane exposed BiOCl nanoplatelets, although In + The energy band of the BiOCl nano-sheet with the oxygen-containing vacancy exposed by the doped (001) crystal face has no obvious change, but has stronger impurity energy level absorption phenomenon in the visible light range.
In fig. 6, the comparison graph of the effect of the BiOCl nano-sheet on degrading the pesticide sodium pentachlorophenate under the visible light shows that the activity of the photocatalyst is tested by degrading the pesticide sodium pentachlorophenate under the visible light, wherein a 500W xenon lamp is used as a light source, and a filter is added to filter out the light with the wavelength less than 420 nm, so that the visible light is obtained. The catalyst was used in an amount of 0.05 g, the concentration of the sodium pentachlorophenate solution was 20 mg/L, and the volume was 50 mL. As can be seen from the figure, in example 4 after half an hour of irradiation with visible light + Doping of the (001) plane-exposed oxygen-containing vacancy BiOCl nanoplatelets resulted In almost complete degradation of sodium pentachlorophenate at a rate of 6.8 times that of the (001) plane-exposed oxygen-containing vacancy BiOCl nanoplatelets of example 1, in of example 2 3+ The doped (001) crystal plane exposes 27.4 times of the BiOCl nanoplatelets.
For In prepared In examples 3,4,5 and 6 + The comparison of the photocatalytic activity of the sample doped with the (001) crystal face and exposed to the oxygen-containing vacancy BiOCl nanosheet (as shown in fig. 7) can be seen that the sample prepared by ultraviolet irradiation for 1 hour in example 3 has the weakest photocatalytic activity, the efficiency of photocatalytic degradation of the insecticide sodium pentachlorophenate under the visible light of the sample above 2 hours of ultraviolet irradiation is equivalent, and the influence of the changes of the three conditions on the catalytic activity is not obvious in the proportion range of ethylene glycol and water, the proportion range of bismuth element and indium element and the dissolution heat reaction temperature range.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalent changes and variations in the above-mentioned embodiments can be made by those skilled in the art without departing from the scope of the present invention.
Claims (2)
1.In + The preparation method of the doped (001) crystal face exposed oxygen-containing vacancy BiOCl nano-sheet is characterized by comprising the following steps:
1) Bismuth nitrate, indium nitrate and potassium chloride are added into a mixed solution of water and glycol, 40mL of suspension is formed under magnetic stirring, wherein the volume ratio of water to glycol is 1: 8-1: 3, a step of;
2) Placing the suspension obtained in the step 1) into a polytetrafluoroethylene reaction kettle, and standing for 10-30 hours in an atmosphere at 160-180 ℃ 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 the BiOCl nano-sheet sample;
4) Irradiating the sample obtained In the step 3) with ultraviolet light to obtain In with a sheet size of less than 200nm and a thickness of 15-25 nm + Doping (001) crystal face to expose oxygen-containing vacancy BiOCl nano-sheet; wherein the sum of the amounts of bismuth nitrate and indium nitrate in the step 1) is equal to the amount of potassium chloride, and the ratio of the amount of indium element to the amount of bismuth element is 1: 100-5: 100;
the ultraviolet irradiation in the step 4) is carried out at room temperature, the sample is within 10cm from the light source and continuously irradiates 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 365nm.
2. In as claimed In claim 1 + The application of the BiOCl nano-sheet with the oxygen-containing vacancy exposed by the doped (001) crystal face is characterized in that: the In is + The (001) crystal face-doped oxygen-containing vacancy BiOCl nano-sheet is used as a visible light catalyst.
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