CN108855194B - Nitrogen-doped nano BiOX type photocatalyst with high catalytic activity and preparation method thereof - Google Patents
Nitrogen-doped nano BiOX type photocatalyst with high catalytic activity and preparation method thereof Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
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- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011324 bead Substances 0.000 claims abstract description 25
- 239000000084 colloidal system Substances 0.000 claims abstract description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 49
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 48
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000001569 carbon dioxide Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 24
- 239000000155 melt Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000000889 atomisation Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 239000011343 solid material Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 16
- 239000004065 semiconductor Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229940073609 bismuth oxychloride Drugs 0.000 description 4
- 239000010842 industrial wastewater Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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Abstract
The invention provides nitrogen with high catalytic activityA doped nano BiOX type photocatalyst and a preparation method thereof relate to the technical field of photocatalysis and have a molecular formula of (BiOX)1‑YNYX is any one of Cl, Br and I, Y is 0.25-0.35%, and the preparation method comprises the following steps: heating and melting refined bismuth, introducing nitrogen, and continuously heating to obtain a superheated melt; atomizing and crushing to obtain superfine molten beads, and burning to obtain liquid Bi2O3(ii) a Adding the mixture into excessive HX, and dropwise adding ammonia water to obtain BiOX colloid; preparing a BiOX gel; and carrying out nitrogen doping reaction for 10-15min, obtaining the nitrogen-doped nano BiOX type photocatalyst after the reaction is finished, wherein after the nitrogen doping, new impurity energy levels are generated between band gap steps due to the introduction of impurity states, the number of energy band layers is correspondingly increased, the impurity energy levels are used as intermediate energy levels, and electrons can be effectively assisted to jump from a valence band to a conduction band, so that the electron mobility is improved, the impurity energy levels can capture electrons, the separation rate of electrons and holes is improved, and the catalytic activity of the photocatalyst is improved.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity and a preparation method thereof.
Background
The photocatalysis technology can directly convert solar energy into chemical energy and electric energy through semiconductor photocatalysis materials, can realize complete mineralization and degradation on toxic and harmful organic pollutants in the environment,
the principle is that a semiconductor is used as a catalyst, an energy band occupied by valence electrons of the semiconductor is called a valence band, an adjacent higher energy band, namely an excited state, is called a conduction band, a forbidden band exists between the valence band and the energy band, when light with energy larger than the forbidden band is irradiated, photoelectrons with energy larger than the forbidden band are absorbed, electrons of the valence band are excited to the conduction band, electrons are carried in the conduction band, holes are generated in the valence band, the electrons have reducibility, the holes have oxidability, the holes have extremely strong ability of acquiring the electrons, and OH-and H-in water can be absorbed by the holes2O is oxidized into OH free radical with strong oxidizing property, the OH free radical has reaction energy of 402MJ/mol, can destroy C-C, C-H, C-O, C-N, N-H bond in organic matter, and oxidize a plurality of refractory organic matters into CO2And H2And O and the like, which is considered to be one of the most potential technical schemes for solving the energy and environmental problems of the human society at present.
Fujishima first proposed the concept of photocatalytic oxidation in 1972, and attracted extensive attention from researchers in various aspects such as chemistry, physics, materials, energy, environment and the like. Among them, studies on modification of photocatalysts (improvement of photocatalytic activity and enlargement of light absorption range), especially, studies on modification by ion doping, have been the focus of attention of broad researchers.
In recent years, scholars at home and abroad have developed a plurality of novel photocatalytic materials, such as layered compounds, structural novel compounds, metal hydroxides, multi-element metal oxides and the like, wherein a representative bismuth oxyhalide BiOX (X ═ Cl, Br, I) photocatalytic material in the layered compounds, especially BiOCl semiconductor materials, show unique layered structures, electronic characteristics, optical properties and good photocatalytic activity and stability, and attract great attention of scientists at home and abroad in the field of photocatalysis, and the doping modification research on the material is one of development projects with great potential in a period of time in the future.
The patent with application publication number CN 106984338A discloses a method for preparing a semiconductor BiOxCyy type photocatalyst by using industrial wastewater, which comprises the steps of adding bismuth nitrate pentahydrate into the industrial wastewater, carrying out ultrasonic treatment in an ultrasonic machine with the power of 100Hz and stirring for 30min to uniformly disperse the bismuth nitrate pentahydrate in the industrial wastewater, then transferring all mixed solution of the industrial wastewater and the bismuth nitrate pentahydrate into a reaction kettle, screwing the reaction kettle, then placing the reaction kettle into a homogeneous reactor, and heating under a certain temperature condition to prepare the semiconductor BiOxCyy type photocatalyst with high photocatalytic activity. The photocatalytic activity of the prepared semiconductor BiOxCly type photocatalyst under the irradiation of ultraviolet light is obviously higher than that of P25 type titanium dioxide and bismuth oxychloride semiconductor photocatalyst; in the process of preparing the semiconductor BiOxCly type photocatalyst, COD, sodium chloride and other pollutants which are difficult to treat in the wastewater are obviously reduced, meanwhile, most of total phosphorus is converted into orthophosphate, and the photocatalytic activity of the orthophosphate can be further improved through doping modification, so that the sewage treatment capacity is improved.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity and a preparation method thereof.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
nitrogen with high catalytic activityDoped nanometer BiOX type photocatalyst with molecular formula of (BiOX)1-YNYX is any one of Cl, Br and I, and Y is 0.25-0.35%.
The preparation method of the nitrogen-doped nano BiOX type photocatalyst with high catalytic activity comprises the following steps:
(1) heating refined bismuth to 280-plus-300 ℃ for melting to obtain a melt, continuously introducing nitrogen into the melt, keeping the temperature and stirring for 20-50min, and then continuously heating to 860-plus-950 ℃ to obtain a superheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe, atomized gas is used for continuously crushing the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring the liquid Bi at a high speed of 800r/min under 600-2O3Adding into excess HX at 60-80 deg.C to obtain clear solution, adding dropwise ammonia water, stirring for 20-40min, reducing rotation speed to 400r/min, continuing stirring for 20-40min, and finally reducing rotation speed to 100r/min, at this time, naturally cooling to obtain BiOX colloid;
(4) centrifuging BiOX colloid at 4000-6000r/min for 10-20min, and washing the centrifuged solid material with distilled water and absolute ethyl alcohol for 3 times respectively;
(5) under the conditions that the pressure is 8-10MPa, the temperature is 35 ℃ and the carbon dioxide flow is 5-10m/s, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOX gel;
(6) and (3) placing the BiOX gel in a reactor, uniformly carrying out contact reaction with non-equilibrium nitrogen direct current plasma arc under normal pressure, carrying out nitrogen doping reaction for 10-15min, and obtaining the nitrogen-doped nano BiOX photocatalyst after the reaction is finished.
Further, the flow rate of the nitrogen gas is 2 to 5 m/s.
Further, the diameter of the draft tube is 1-4 mm.
Further, the atomizing gas is any one of air, nitrogen and argon.
Further, the flow velocity of the atomizing gas is 60 to 100 m/s.
Further, the temperature of the atomizing gas is 80-100 ℃.
Further, the HX is any one of HCl, HBr and HI.
Further, the mass concentration of the ammonia water is 15-25%.
(III) advantageous effects
The invention provides a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity and a preparation method thereof, and the photocatalyst has the following beneficial effects:
BiOX belongs to a tetragonal crystal system structure, and double X in the crystal-Ionic layer and [ Bi2O2]2+The layers are alternately arranged to form a layered structure, the structure is loose through non-bonding force combination, an electrostatic sub-field is arranged in the middle, the effective separation of photoelectron-hole pairs is facilitated, Cl, Br and I belong to the same group elements, the rejection is small, in addition, the respective band gaps (3.40eV, 2.92eV and 1.85eV) of BiOCl, BiOBr and BiOI are moderate, a certain band gap step can be formed, the solar energy of different wave bands can be ensured to be absorbed, after BiOX is doped with nitrogen, new impurity energy levels are generated among the band gap steps due to the introduction of impurity states, on one hand, the number of energy band layers is correspondingly increased and becomes more compact, the impurity energy levels are used as middle energy levels, electrons can be effectively assisted to transfer from a valence band to a conduction band, so that the electron mobility is improved, on the other hand, the impurity energy levels can be used as shallow donor levels to capture electrons, and prolong the recombination time of photo, the separation rate of electrons and holes is improved, and the catalytic activity of the photocatalyst is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity is characterized in that the molecular formula is (BiOCl)1- YNYAnd Y is 0.28%.
The preparation method comprises the following steps:
(1) heating refined bismuth to 280 ℃ to melt to obtain a melt, continuously introducing nitrogen gas of 4m/s into the melt, keeping the temperature and stirring for 40min, and continuously heating to 870 ℃ to obtain an overheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe with the diameter of 2mm, nitrogen with the flow rate of 80m/s and the temperature of 85 ℃ is utilized to continuously break the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring liquid Bi at high speed of 700r/min2O3Adding into 65 ℃ excess HCl to obtain a clear solution, then dropwise adding ammonia water with the mass concentration of 20%, stirring for 30min, reducing the rotating speed to 400r/min, continuing stirring for 20min, finally reducing the rotating speed to 100r/min, and naturally cooling to obtain a BiOCl colloid;
(4) centrifuging the BiOCl colloid for 15min at the speed of 4000r/min, and washing the centrifuged solid material with distilled water and absolute ethyl alcohol for 3 times respectively;
(5) under the conditions of 8.5MPa of pressure, 35 ℃ of temperature and 5m/s of carbon dioxide flow, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOCl gel;
(6) and (3) placing the BiOCl gel into a reactor, uniformly carrying out contact reaction with non-equilibrium nitrogen direct-current plasma arc under normal pressure, carrying out nitrogen doping reaction for 10min, and obtaining the nitrogen-doped nano BiOCl type photocatalyst after the reaction is finished.
Example 2:
a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity is characterized in that the molecular formula is (BiOBr)1- YNYAnd Y is 0.25%.
The preparation method comprises the following steps:
(1) heating refined bismuth to 290 ℃ to melt to obtain a melt, continuously introducing 5m/s of nitrogen into the melt, keeping the temperature and stirring for 50min, and continuously heating to 900 ℃ to obtain an overheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe with the diameter of 2mm, nitrogen with the flow rate of 80m/s and the temperature of 90 ℃ is utilized to continuously break the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring liquid Bi at high speed of 700r/min2O3Adding into 65 ℃ excess HCl to obtain a clear solution, then dropwise adding 23% ammonia water, stirring for 25min, reducing the rotating speed to 400r/min, continuing stirring for 30min, finally reducing the rotating speed to 100r/min, and naturally cooling to obtain a BiOBr colloid;
(4) centrifuging the BiOBr colloid at 4500r/min for 15min, and washing the centrifuged solid material with distilled water and anhydrous ethanol for 3 times respectively;
(5) under the conditions that the pressure is 8.5MPa, the temperature is 35 ℃ and the carbon dioxide flow is 8m/s, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOBr gel;
(6) and (3) placing the BiOBr gel in a reactor, uniformly carrying out contact reaction with the non-equilibrium nitrogen direct-current plasma arc under normal pressure, carrying out nitrogen doping reaction for 12min, and obtaining the nitrogen-doped nano BiOBr type photocatalyst after the reaction is finished.
Example 3:
a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity is characterized in that the molecular formula is (BiOI)1- YNYAnd Y is 0.33%.
The preparation method comprises the following steps:
(1) heating refined bismuth to 300 ℃ to melt to obtain a melt, continuously introducing 5m/s of nitrogen into the melt, keeping the temperature and stirring for 50min, and continuously heating to 920 ℃ to obtain an overheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe with the diameter of 4mm, nitrogen with the flow rate of 90m/s and the temperature of 100 ℃ is utilized to continuously break the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring the liquid Bi at high speed of 750r/min2O3Adding into 75 ℃ excessive HI to obtain a clear solution, then dropwise adding 25% ammonia water, stirring for 40min, reducing the rotating speed to 400r/min, continuing stirring for 40min, finally reducing the rotating speed to 100r/min, and naturally cooling to obtain the BiOI colloid;
(4) centrifuging the BiOI colloid at 6000r/min for 20min, and washing the centrifuged solid material with distilled water and absolute ethyl alcohol for 3 times respectively;
(5) under the conditions of pressure intensity of 9MPa, temperature of 35 ℃ and carbon dioxide flow rate of 8m/s, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOI gel;
(6) and (3) placing the BiOI gel into a reactor, uniformly carrying out arc contact reaction with non-equilibrium nitrogen direct-current plasma under normal pressure, carrying out nitrogen doping reaction for 15min, and obtaining the nitrogen-doped nano BiOI photocatalyst after the reaction is finished.
Example 4:
a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity is characterized in that the molecular formula is (BiOCl)1- YNYAnd Y is 0.35%.
The preparation method comprises the following steps:
(1) heating refined bismuth to 280 ℃ to melt to obtain a melt, continuously introducing 2m/s of nitrogen into the melt, keeping the temperature and stirring for 20min, and continuously heating to 860 ℃ to obtain a superheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe with the diameter of 1mm, nitrogen with the flow rate of 60m/s and the temperature of 80 ℃ is utilized to continuously break the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring the liquid Bi at a high speed of 600r/min2O3Adding into excess HCl at 60 ℃ to obtain a clear solution, then dropwise adding ammonia water with the mass concentration of 15%, stirring for 20min, reducing the rotating speed to 400r/min, continuing stirring for 20min, finally reducing the rotating speed to 100r/min, and naturally cooling to obtain BiOCl colloid;
(4) centrifuging the BiOCl colloid at 4000r/min for 10min, and washing the centrifuged solid material with distilled water and absolute ethyl alcohol for 3 times respectively;
(5) under the conditions of 8MPa of pressure, 35 ℃ of temperature and 5m/s of carbon dioxide flow, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOCl gel;
(6) and (3) placing the BiOCl gel into a reactor, uniformly carrying out contact reaction with non-equilibrium nitrogen direct-current plasma arc under normal pressure, carrying out nitrogen doping reaction for 10min, and obtaining the nitrogen-doped nano BiOCl type photocatalyst after the reaction is finished.
Example 5:
a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity is characterized in that the molecular formula is (BiOCl)1- YNYAnd Y is 0.30%.
The preparation method comprises the following steps:
(1) heating refined bismuth to 300 ℃ to melt to obtain a melt, continuously introducing 5m/s of nitrogen into the melt, keeping the temperature and stirring for 50min, and continuously heating to 950 ℃ to obtain a superheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe with the diameter of 4mm, nitrogen with the flow rate of 100m/s and the temperature of 100 ℃ is utilized to continuously break the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring liquid Bi at high speed of 800r/min2O3Adding into excess HCl of 80 deg.C to obtain clear solution, adding dropwise 25% ammonia water, stirring for 40min, and reducing rotation speed to 40%Stirring for 40min at the speed of 0r/min, and finally, reducing the rotating speed to 100r/min, and naturally cooling to obtain BiOCl colloid;
(4) centrifuging the BiOCl colloid at 6000r/min for 20min, and washing the centrifuged solid material with distilled water and anhydrous ethanol for 3 times respectively;
(5) under the conditions of 10MPa of pressure, 35 ℃ of temperature and 10m/s of carbon dioxide flow, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOCl gel;
(6) and (3) placing the BiOCl gel into a reactor, uniformly carrying out contact reaction with non-equilibrium nitrogen direct-current plasma arc under normal pressure, carrying out nitrogen doping reaction for 15min, and obtaining the nitrogen-doped nano BiOCl type photocatalyst after the reaction is finished.
Example 6:
a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity is characterized in that the molecular formula is (BiOBr)1- YNYAnd Y is 0.25%.
The preparation method comprises the following steps:
(1) heating refined bismuth to 300 ℃ to melt to obtain a melt, continuously introducing 5m/s of nitrogen into the melt, keeping the temperature and stirring for 40min, and continuously heating to 870 ℃ to obtain an overheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe with the diameter of 3mm, nitrogen with the flow rate of 85m/s and the temperature of 95 ℃ is utilized to continuously break the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring the liquid Bi at a high speed of 600r/min2O3Adding into excess HBr at 70 ℃ to obtain a clear solution, then dropwise adding ammonia water with the mass concentration of 18%, stirring for 40min, reducing the rotating speed to 400r/min, continuing stirring for 30min, finally reducing the rotating speed to 100r/min, and naturally cooling to obtain BiOBr colloid;
(4) centrifuging the BiOBr colloid at 5500r/min for 12min, and washing the centrifuged solid material with distilled water and absolute ethyl alcohol for 3 times respectively;
(5) under the conditions that the pressure is 8.5MPa, the temperature is 35 ℃ and the carbon dioxide flow is 9m/s, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOBr gel;
(6) and (3) placing the BiOBr gel in a reactor, uniformly carrying out contact reaction with the non-equilibrium nitrogen direct-current plasma arc under normal pressure, carrying out nitrogen doping reaction for 13min, and obtaining the nitrogen-doped nano BiOBr type photocatalyst after the reaction is finished.
Example 7:
a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity is characterized in that the molecular formula is (BiOCl)1- YNYAnd Y is 0.32%.
The preparation method comprises the following steps:
(1) heating refined bismuth to 300 ℃ to melt to obtain a melt, continuously introducing 2m/s of nitrogen into the melt, keeping the temperature and stirring for 50min, and continuously heating to 860 ℃ to obtain a superheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe with the diameter of 1mm, nitrogen with the flow rate of 60m/s and the temperature of 100 ℃ is utilized to continuously break the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring the liquid Bi at a high speed of 600r/min2O3Adding into excess HCl at the temperature of 80 ℃ to obtain a clear solution, then dropwise adding ammonia water with the mass concentration of 15%, stirring for 20min, reducing the rotating speed to 400r/min, continuing stirring for 40min, finally reducing the rotating speed to 100r/min, and naturally cooling to obtain BiOCl colloid;
(4) centrifuging the BiOCl colloid at 4000r/min for 10min, and washing the centrifuged solid material with distilled water and absolute ethyl alcohol for 3 times respectively;
(5) under the conditions of 10MPa of pressure, 35 ℃ of temperature and 5m/s of carbon dioxide flow, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOCl gel;
(6) and (3) placing the BiOCl gel into a reactor, uniformly carrying out contact reaction with non-equilibrium nitrogen direct-current plasma arc under normal pressure, carrying out nitrogen doping reaction for 10min, and obtaining the nitrogen-doped nano BiOCl type photocatalyst after the reaction is finished.
Example 8:
a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity is characterized in that the molecular formula is (BiOI)1- YNYAnd Y is 0.25%.
The preparation method comprises the following steps:
(1) heating refined bismuth to 300 ℃ to melt to obtain a melt, continuously introducing 5m/s of nitrogen into the melt, keeping the temperature and stirring for 40min, and continuously heating to 880 ℃ to obtain a superheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe with the diameter of 3mm, nitrogen with the flow rate of 85m/s and the temperature of 100 ℃ is utilized to continuously break the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring the liquid Bi at a high speed of 600r/min2O3Adding into 75 ℃ excessive HI to obtain a clear solution, then dropwise adding ammonia water with the mass concentration of 20%, stirring for 30min, reducing the rotating speed to 400r/min, continuing stirring for 40min, finally reducing the rotating speed to 100r/min, and naturally cooling to obtain the BiOI colloid;
(4) centrifuging the BiOI colloid for 15min at a speed of 5500r/min, and washing the centrifuged solid material for 3 times by using distilled water and absolute ethyl alcohol respectively;
(5) under the conditions of 10MPa of pressure, 35 ℃ of temperature and 8m/s of carbon dioxide flow, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOI gel;
(6) and (3) placing the BiOI gel into a reactor, uniformly carrying out arc contact reaction with non-equilibrium nitrogen direct-current plasma under normal pressure, carrying out nitrogen doping reaction for 15min, and obtaining the nitrogen-doped nano BiOI photocatalyst after the reaction is finished.
Example 9:
a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity is characterized in that the molecular formula is (BiOCl)1- YNYAnd Y is 0.35%.
The preparation method comprises the following steps:
(1) heating refined bismuth to 300 ℃ to melt to obtain a melt, continuously introducing 5m/s of nitrogen into the melt, keeping the temperature and stirring for 50min, and continuously heating to 860 ℃ to obtain a superheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe with the diameter of 1mm, argon with the flow rate of 60m/s and the temperature of 85 ℃ is used for continuously crushing the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring liquid Bi at high speed of 700r/min2O3Adding into 65 ℃ excess HCl to obtain a clear solution, then dropwise adding 23% ammonia water, stirring for 40min, reducing the rotating speed to 400r/min, continuing stirring for 28min, finally reducing the rotating speed to 100r/min, and naturally cooling to obtain BiOCl colloid;
(4) centrifuging the BiOCl colloid for 16min at the speed of 4000r/min, and washing the centrifuged solid material with distilled water and absolute ethyl alcohol for 3 times respectively;
(5) under the conditions that the pressure is 8.5MPa, the temperature is 35 ℃ and the carbon dioxide flow is 6m/s, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOCl gel;
(6) and (3) placing the BiOCl gel into a reactor, uniformly carrying out contact reaction with non-equilibrium nitrogen direct-current plasma arc under normal pressure, carrying out nitrogen doping reaction for 15min, and obtaining the nitrogen-doped nano BiOCl type photocatalyst after the reaction is finished.
Example 10:
a nitrogen-doped nano BiOX type photocatalyst with high catalytic activity is characterized in that the molecular formula is (BiOCl)1- YNYAnd Y is 0.33%.
The preparation method comprises the following steps:
(1) heating refined bismuth to 300 ℃ to melt to obtain a melt, continuously introducing nitrogen gas of 4m/s into the melt, keeping the temperature and stirring for 35min, and continuously heating to 880 ℃ to obtain a superheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe with the diameter of 4mm, the superheated melt trickle is continuously crushed by utilizing air with the flow rate of 100m/s and the temperature of 100 ℃ to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring the liquid Bi at a high speed of 600r/min2O3Adding into 65 ℃ excess HCl to obtain a clear solution, then dropwise adding 15-25% ammonia water, stirring for 35min, reducing the rotating speed to 400r/min, continuing stirring for 20min, finally reducing the rotating speed to 100r/min, and naturally cooling to obtain a BiOCl colloid;
(4) centrifuging the BiOCl colloid at 4000r/min for 10min, and washing the centrifuged solid material with distilled water and absolute ethyl alcohol for 3 times respectively;
(5) under the conditions of 10MPa of pressure, 35 ℃ of temperature and 8m/s of carbon dioxide flow, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOCl gel;
(6) and (3) placing the BiOCl gel into a reactor, uniformly carrying out contact reaction with non-equilibrium nitrogen direct-current plasma arc under normal pressure, carrying out nitrogen doping reaction for 12min, and obtaining the nitrogen-doped nano BiOCl type photocatalyst after the reaction is finished.
Photocatalytic reaction degradation experiment:
the degradation performance of the nitrogen-doped nano BiOCl photocatalyst prepared in the embodiment 1 of the invention is compared with the degradation performance of nano bismuth oxide and nano bismuth oxychloride in the photocatalytic reaction, and the specific results are shown in the following tables 1 and 2:
table 1:
reaction conditions are as follows: the reaction is carried out in a quartz reaction tube, the concentration of methylene blue is 6mg/L, the nitrogen-doped nano BiOCl type photocatalyst, nano bismuth oxide and nano bismuth oxychloride are all 100mg, suspension is prepared, and H is added2O22ml, and the reaction is performed for 40min by illumination.
Table 2:
reaction conditions are as follows: the reaction is carried out in a quartz reaction tube, the concentration of methylene blue is 6mg/L, the nitrogen-doped nano BiOCl type photocatalyst, nano bismuth oxide and nano bismuth oxychloride are all 100mg, suspension is prepared, and H is added2O22ml, light reaction, and observing the color change of the suspension.
According to experimental results, the embodiment of the invention has the advantages of short degradation time and high degradation rate.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of a nitrogen-doped nano BiOX photocatalyst with high catalytic activity is characterized by comprising the following steps:
(1) heating refined bismuth to 280-plus-300 ℃ for melting to obtain a melt, continuously introducing nitrogen into the melt, keeping the temperature and stirring for 20-50min, and then continuously heating to 860-plus-950 ℃ to obtain a superheated melt;
(2) the superheated melt enters an atomization device through a flow guide pipe, atomized gas is used for continuously crushing the superheated melt trickle to obtain superfine molten beads, and the superfine molten beads are combusted in oxygen to obtain liquid Bi2O3；
(3) Stirring the liquid Bi at a high speed of 800r/min under 600-2O3Adding into excess HX at 60-80 deg.C to obtain clear solution, adding dropwise ammonia water, stirring for 20-40min, reducing rotation speed to 400r/min, continuing stirring for 20-40min, and finally reducing rotation speed to 100r/min, at this time, naturally cooling to obtain BiOX colloid;
(4) centrifuging BiOX colloid at 4000-6000r/min for 10-20min, and washing the centrifuged solid material with distilled water and absolute ethyl alcohol for 3 times respectively;
(5) under the conditions that the pressure is 8-10MPa, the temperature is 35 ℃ and the carbon dioxide flow is 5-10m/s, replacing absolute ethyl alcohol with liquid carbon dioxide, recovering normal pressure, naturally cooling to room temperature, and calcining at 450 ℃ for 150min to obtain BiOX gel;
(6) placing the BiOX gel in a reactor, uniformly performing arc contact reaction with non-equilibrium nitrogen direct current plasma at normal pressure, performing nitrogen doping reaction for 10-15min, and obtaining nitrogen-doped nano BiOX type photocatalyst with molecular formula of (BiOX)1-YNYX is any one of Cl, Br and I, and Y is 0.25-0.35%.
2. The method of preparing a nitrogen-doped nano BiOX-type photocatalyst as claimed in claim 1, wherein the flow rate of the nitrogen gas is 2-5 m/s.
3. The method of preparing a nitrogen-doped nano BiOX type photocatalyst as claimed in claim 1, wherein the diameter of the draft tube is 1-4 mm.
4. The method of preparing a nitrogen-doped nano BiOX type photocatalyst as claimed in claim 1, wherein the atomizing gas is any one of air, nitrogen and argon.
5. The method of preparing a nitrogen-doped nano BiOX type photocatalyst as claimed in claim 1, wherein the flow rate of the atomizing gas is 60-100 m/s.
6. The method of preparing a nitrogen-doped nano BiOX type photocatalyst as claimed in claim 1, wherein the temperature of the atomizing gas is 80-100 ℃.
7. The method of claim 1, wherein the HX is any one of HCl, HBr, and HI.
8. The method of preparing a nitrogen-doped nano BiOX type photocatalyst as claimed in claim 1, wherein the mass concentration of the ammonia water is 15-25%.
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