CN115007178B - Preparation method and application of high-stability bismuth oxychloride photocatalytic material - Google Patents
Preparation method and application of high-stability bismuth oxychloride photocatalytic material Download PDFInfo
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- CN115007178B CN115007178B CN202210946704.2A CN202210946704A CN115007178B CN 115007178 B CN115007178 B CN 115007178B CN 202210946704 A CN202210946704 A CN 202210946704A CN 115007178 B CN115007178 B CN 115007178B
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000000463 material Substances 0.000 title claims abstract description 119
- 229940073609 bismuth oxychloride Drugs 0.000 title claims abstract description 116
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 59
- 239000012266 salt solution Substances 0.000 claims abstract description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- 238000007710 freezing Methods 0.000 claims abstract description 23
- 230000008014 freezing Effects 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 5
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000000227 grinding Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 8
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 230000006798 recombination Effects 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 239000008367 deionised water Substances 0.000 description 41
- 229910021641 deionized water Inorganic materials 0.000 description 41
- 238000001035 drying Methods 0.000 description 40
- 239000000523 sample Substances 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 239000012535 impurity Substances 0.000 description 21
- 238000005406 washing Methods 0.000 description 21
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- 238000000034 method Methods 0.000 description 15
- 239000011941 photocatalyst Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
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- 229910052721 tungsten Inorganic materials 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 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 4
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000002003 electron diffraction Methods 0.000 description 3
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- 235000011187 glycerol Nutrition 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution 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
Images
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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
- B01J27/06—Halogens; Compounds thereof
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of a high-stability bismuth oxychloride photocatalytic material, and belongs to the technical field of photocatalytic materials. The preparation method of the high-stability bismuth oxychloride photocatalytic material comprises the following steps: and quickly pouring a rare metal salt solution into the bismuth source powder, separating out a precipitate after ultrasonic stirring, freezing by using liquid nitrogen, and then carrying out vacuum freeze drying to obtain the high-stability bismuth oxychloride photocatalytic material. The high-stability bismuth oxychloride photocatalytic material prepared by the invention has high photocatalytic hydrogen production performance, can ensure that the photocatalytic hydrogen production reaction is stably carried out, and effectively solves the unstable problems of high bismuth oxychloride photogenerated carrier recombination rate, serious photo-corrosion and the like.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a preparation method and application of a high-stability bismuth oxychloride photocatalytic material.
Background
With the development of human society, the living standard of human beings is continuously improved by more efficient scientific technology and higher industrial agriculture degree, and the traveling and communication become more convenient and faster, and the two problems of environmental pollution, energy exhaustion and the like are also faced. To solve this problem, many methods have been developed. The solar energy is used as the main energy of the outer space, and the energy radiated by the sun greatly exceeds the global annual energy demand. Due to the long life expectancy of the sun, solar energy is also considered as a renewable energy source which can be harvested on the earth, and is an important energy source beneficial to the harmonious development of human and nature. Discovery of TiO by Fujishima and Honda since 1972 2 The electrode is used for decomposing water to prepare hydrogen under ultraviolet light and treating pollutants in waterPhotocatalytic technology of conductors has been studied as a technology for degrading water pollution and a source of hydrogen energy. Under the action of solar energy, chemical reactions which need to occur under severe conditions are converted to be carried out under a milder environment through a photocatalyst. The method not only can be used for preparing hydrogen by decomposing water through photocatalysis, but also can realize the degradation of pollutants and the fixation of carbon dioxide, and has great potential for improving and relieving the current environmental pollution, greenhouse effect and energy problems. Therefore, the semiconductor photocatalysis technology has important application prospect in the fields of energy and environment.
Among many visible light-responsive photocatalytic materials, the photocatalyst of bismuth-based metal oxide semiconductor material is considered by the researchers to be a promising substitute for TiO due to the narrow band gap, the long available visible light band, the high catalytic activity and the like 2 One of the photocatalysts of the narrow bandgap semiconductor material of (1). In recent years, biOCl nano-materials have attracted much attention due to their unique layered structure. BiOCl is a compound of [ Bi ] 2 O 2 ] 2+ Layer and two Cl - The layers make up to form a homogenous "sandwich" structure that can achieve good space charge separation and is of great interest to researchers in the field of photocatalysis. However, on one hand, the distance of the photon-generated carriers in the BiOCl phase is too long, so that the recombination rate is high, and on the other hand, the photoresponse range is narrow due to the wider band gap. Most importantly, the structural instability of BiOCl is easily corroded by light, so that the photocatalytic activity of BiOCl is low, and the application of BiOCl in photocatalysis is seriously influenced.
In order to promote the practical application of BiOCl in photocatalysis, it is very important to improve the stability of BiOCl. At present, a plurality of traditional modification means such as morphology regulation, semiconductor compounding, defect structure and the like are applied to the research of improving the performance of the BiOCl photocatalyst, and certain effect is achieved. Compared with other traditional modification means, the method for doping the metal element into the catalyst is an effective modification means for improving the stability of the photocatalyst and the separation efficiency of the photogenerated carrier. Since the rise of the photocatalytic technology in 1972, the research on photocatalysts at home and abroad focuses on how to realize efficient separation of photon-generated carriers and improve the stability of the catalyst, and element doping of the catalyst is an effective means. In the prior art, research on doping is basically surrounded by complex and tedious methods such as a hydrothermal method, a solvothermal method, a molten salt method and the like. How to simplify the preparation method of the BiOCl photocatalytic material and solve the problems of narrow response range, high recombination rate of photon-generated carriers, serious photo-corrosion and the like of the BiOCl photocatalytic material becomes a technical problem to be solved urgently by technical personnel in the field.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-stability bismuth oxychloride photocatalytic material, and aims to solve the problems in the prior art. In addition, the preparation method of the invention has the advantages of simple operation, cheap raw materials and short reaction time, and can be used for large-scale production.
In order to achieve the purpose, the invention provides the following scheme:
one of the technical schemes of the invention is as follows: a preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
and quickly pouring a rare metal salt solution into the bismuth source powder, separating out a precipitate after ultrasonic stirring, freezing with liquid nitrogen, and then carrying out vacuum freeze drying to obtain the high-stability bismuth oxychloride photocatalytic material.
Further, the preparation of the rare metal salt solution specifically comprises: adding rare metal salt into water, and stirring to obtain the rare metal salt solution.
Further, the rare metal salt comprises one or more of sodium tungstate, sodium metatungstate, white tungstic acid, sodium vanadate and molybdic acid; the stirring speed is 100 to 400r/min, and the stirring time is 25 to 35min.
Further, the preparation of the bismuth source powder specifically comprises: grinding a bismuth source under an anhydrous condition until the particle size is 200-500nm to obtain bismuth source powder.
Further, the ambient temperature of the milling is room temperature.
The bismuth source is stored under anhydrous conditions prior to grinding.
Further, the bismuth source includes bismuth chloride (autohydrolysis).
Further, the mass ratio of the bismuth source powder to the rare metal salt in the rare metal salt solution is 0.9 to 22.5.
Further, the temperature of the vacuum freeze drying is-52 to-48 ℃, and the time is 45 to 50h.
Further, the time of ultrasonic stirring is 10 to 30min.
Further, the temperature of the ultrasonic agitation is room temperature.
The second technical scheme of the invention is as follows: a high-stability bismuth oxychloride photocatalytic material prepared by the preparation method.
The third technical scheme of the invention is as follows: the application of the high-stability bismuth oxychloride photocatalytic material in photocatalysis.
The invention discloses the following technical effects:
(1) The high-stability bismuth oxychloride photocatalytic material prepared by the invention has high photocatalytic hydrogen production performance, can ensure that the photocatalytic hydrogen production reaction is stably carried out, and effectively solves the unstable problems of high bismuth oxychloride photogenerated carrier recombination rate, serious photo-corrosion and the like.
(2) The preparation method prepares the metal element doped (tungsten, vanadium and molybdenum) bismuth oxychloride photocatalytic material by a simple self-hydrolysis-freeze drying method, has simple and controllable preparation process, and is beneficial to mass production and popularization. After the metal element is doped, on one hand, the defect energy level formed by doping can widen the photoresponse range of the photocatalyst, on the other hand, a large number of unsaturated sites and defects generally exist around the doped atoms, the unsaturated sites can be sometimes used as reactive active sites, and some defects can be used as traps to repeatedly capture and release photon-generated electrons/holes, so that the separation efficiency of photon-generated carriers is enhanced. In addition, the stable unit structure formed after doping can effectively restrain the unstable structure of the photocatalyst, so that the stability of the photocatalyst is improved, and the photocatalytic efficiency is improved to a certain extent. The problems of narrow photoresponse range, high photo-generated charge recombination efficiency, instability caused by serious photo-corrosion and the like in the prior art are effectively solved.
(3) The invention fills the blank of research on doping by a self-hydrolysis method, and prepares the metal element-doped bismuth oxychloride photocatalytic material by a simple self-hydrolysis-freeze drying method. And the doped metal source and the concentration of the doped metal source in the material preparation process are optimized, and the washing and drying processes are optimally designed after the reaction is finished, so that the metal element doped bismuth oxychloride photocatalytic material with better photocatalytic hydrogen production and organic matter photodegradation performance is further obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of the materials prepared in examples 1 and 2 of the present invention;
FIG. 2 is a scanning electron microscope image of the high-stability bismuth oxychloride photocatalytic material prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of the high-stability bismuth oxychloride photocatalytic material prepared in example 1 of the present invention;
FIG. 4 is an electron diffraction diagram of the high-stability bismuth oxychloride photocatalytic material prepared in example 1 of the present invention;
FIG. 5 is an EDS spectrum of the high-stability bismuth oxychloride photocatalytic material prepared in example 1 of the present invention;
FIG. 6 is a XPS W4f spectrum of the high stability bismuth oxychloride photocatalytic material prepared in example 1 of the present invention;
FIG. 7 is a graph comparing the photocatalytic hydrogen production performance of the materials prepared in examples 1 and 2 of the present invention;
FIG. 8 is a graph showing photocatalytic hydrogen production performance of the materials prepared in examples 11 and 19 of the present invention;
FIG. 9 is a photo-catalytic hydrogen production performance curve diagram of materials prepared in demonstration examples 1 to 3 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
The bismuth sources used in the following examples of the invention were all stored under anhydrous conditions.
Example 1
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 3.15g (0.01 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to obtain bismuth chloride powder (particle size 200 nm).
(2) Adding 0.66g (0.0022 mol) sodium tungstate into 20mL deionized water, and stirring at 400r/min for 30min to obtain the product containing WO 4 2- A metal salt solution of (a).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing by using liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times by using deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (tungsten-doped bismuth oxychloride material).
Example 2
(1) 3.15g (0.01 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to obtain bismuth chloride powder (particle size 200 nm).
(2) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly adding 20mL of deionized water, ultrasonically stirring at room temperature for 10min, separating out a precipitate, freezing by using liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times by using deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the bismuth oxychloride material without any element doping.
FIG. 1 is an X-ray diffraction pattern of the materials prepared in inventive examples 1 and 2, wherein the a-curve is example 1, the b-curve is example 2, and the c-curve is a bismuth oxychloride standard.
As can be seen from FIG. 1, the peak intensity of the tungsten-doped bismuth oxychloride material prepared in the example 1 of the invention is slightly reduced, which shows that the crystallinity of the tungsten-doped bismuth oxychloride material is slightly reduced after doping; the peak position is basically consistent with the characteristic peak position of pure-phase bismuth oxychloride, and other positions have no impurity peaks, which indicates that the prepared sample is pure and does not contain other impurities, so that the material prepared in the embodiment 1 of the invention is a tungsten-doped bismuth oxychloride photocatalytic material.
Fig. 2 is a scanning electron microscope image of the tungsten-doped bismuth oxychloride material prepared in example 1 of the present invention.
As can be seen from fig. 2, the tungsten-doped bismuth oxychloride material prepared in example 1 of the present invention has a two-dimensional sheet-like morphology.
FIG. 3 is a transmission electron microscope image of the tungsten-doped bismuth oxychloride material prepared in example 1 of the present invention; fig. 4 is an electron diffraction diagram of the tungsten-doped bismuth oxychloride material prepared in example 1 of the invention.
As can be seen from fig. 3, the tungsten-doped bismuth oxychloride material prepared in example 1 of the present invention has a two-dimensional sheet shape, which matches with the result of a scanning electron microscope, and in addition, in a high-resolution transmission diagram, the tungsten-doped bismuth oxychloride material shows lattice fringes, and as can be seen from the selected region electron diffraction in fig. 4, the tungsten-doped bismuth oxychloride sample product prepared in example 1 is a single crystal phase.
Fig. 5 is an EDS spectrum of the tungsten-doped bismuth oxychloride material prepared in example 1 of the present invention.
As can be seen from fig. 5, the tungsten-doped bismuth oxychloride material prepared in example 1 of the present invention mainly comprises four elements, i.e., bi, O, cl and W, and it can be observed that the W element is uniformly distributed on the sample, which indicates that the W element has been successfully doped into the material. This is consistent with previous XRD results, which further demonstrate that the sample is a tungsten-doped bismuth oxychloride sample material.
Fig. 6 is a XPS W4f spectrum of the tungsten-doped bismuth oxychloride material prepared in example 1 of the invention.
As can be seen from fig. 6, the tungsten-doped bismuth oxychloride material prepared in example 1 of the present invention has a peak of W4f, and the peak separation fitting result shows that the tungsten atom is doped into the material in a form of forming covalent bonds with other atoms. This is consistent with previous EDS spectra results, further demonstrating that the tungsten element was successfully doped.
The photocatalytic hydrogen production performance of the materials prepared in examples 1 and 2 of the present invention was measured.
The measurement method is as follows:
measuring by adopting a Pofely Labsolar-6A system;
the specific test method comprises the following steps: a10 mg sample was taken, dispersed in 50mL of water containing 5mL of Triethanolamine (TEOA) as a sacrificial agent, 0.3mg of Pt was added as a co-catalyst, the system was evacuated for 60min before light irradiation to remove residual air, a 300W xenon lamp was used as a light source, and the amount of hydrogen generated was quantified by gas chromatography (Shimadzu GC-8A, TCD, ar carrier). The measured hydrogen production data are shown in FIG. 7, wherein the curve d in FIG. 7 is example 1, and the curve e in FIG. 7 is example 2.
As can be seen from FIG. 7, the hydrogen production capacity of the pure-phase bismuth oxychloride of example 2 can only be maintained for 3 hours and the hydrogen production rate is 31.55. Mu. Mol g -1 h -1 While the hydrogen production curve of the tungsten-doped bismuth oxychloride material in the example 1 obviously shows a good linear relationship, and the tungsten-doped bismuth oxychloride material can still keep good hydrogen production capability after 5 hours, wherein the hydrogen production rate is 193.72 mu mol g -1 h -1 6.14 times of pure phase bismuth oxychloride. The method shows that after tungsten doping, the hydrogen production performance of the bismuth oxychloride is improved, the stability is greatly improved, and the problems of high recombination rate of bismuth oxychloride photon-generated carriers, serious light corrosion and the like are effectively solved.
Example 3
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 3.15g (0.01 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to obtain bismuth chloride powder (particle size 200 nm).
(2) Adding 1.32g (0.00022 mol) of sodium metatungstate into 20mL of deionized water, and stirring for 30min at 400r/min to form a mixture containing WO 4 2- The metal salt solution of (2).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times with deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (tungsten-doped bismuth oxychloride material).
Example 4
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 3.15g (0.01 mol) of bismuth chloride was ground at room temperature under anhydrous conditions for 60min to obtain bismuth chloride powder (particle size: 200 nm).
(2) Adding 0.66g (0.0026 mol) of white tungstic acid into 20mL of deionized water, and stirring for 30min at the condition of 400r/min to form the product containing WO 4 2- The metal salt solution of (2).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing by using liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times by using deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (tungsten-doped bismuth oxychloride material).
Example 5
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 3.15g (0.01 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to obtain bismuth chloride powder (particle size 500 nm).
(2) Adding 0.66g (0.0022 mol) sodium tungstate into 50mL deionized water, and stirring at 400r/min for 30min to obtain the product containing WO 4 2- The metal salt solution of (2).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times with deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (tungsten-doped bismuth oxychloride material).
Example 6
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 3.15g (0.01 mol) of bismuth chloride was ground at room temperature under anhydrous conditions for 60min to obtain bismuth chloride powder (particle size 500 nm).
(2) Adding 0.66g (0.0022 mol) sodium tungstate into 20mL deionized water, and stirring at 400r/min for 30min to obtain a mixture containing WO 4 2- The metal salt solution of (2).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 200mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing by using liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times by using deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (tungsten-doped bismuth oxychloride material).
Example 7
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 3.15g (0.01 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to obtain bismuth chloride powder (particle size 200 nm).
(2) Adding 0.66g (0.0022 mol) sodium tungstate into 20mL deionized water, and stirring at 400r/min for 30min to obtain the product containing WO 4 2- The metal salt solution of (2).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring at room temperature for 30min, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying at-50 ℃ for 48h under a vacuum condition, mixing and washing with deionized water and absolute ethyl alcohol for 5 times, removing impurities, drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (tungsten-doped bismuth oxychloride material).
Example 8
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 1.26g (0.004 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to obtain bismuth chloride powder (particle size: 200 nm).
(2) Adding 0.66g (0.0022 mol) sodium tungstate into 20mL deionized water, and stirring at 400r/min for 30min to obtain a mixture containing WO 4 2- The metal salt solution of (2).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times with deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (tungsten-doped bismuth oxychloride material).
Example 9
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 1.26g (0.004 mol) of bismuth chloride was ground at room temperature for 30min under anhydrous conditions to obtain bismuth chloride powder (particle size 500 nm).
(2) Adding 0.66g (0.0022 mol) sodium tungstate into 20mL deionized water, and stirring at 400r/min for 30min to obtain the product containing WO 4 2- The metal salt solution of (2).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing by using liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times by using deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (tungsten-doped bismuth oxychloride material).
Example 10
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 1.26g (0.004 mol) of bismuth chloride was ground at room temperature for 30min under anhydrous conditions to obtain bismuth chloride powder (particle size 500 nm).
(2) Adding 0.66g (0.0022 mol) sodium tungstate into 20mL deionized water, and stirring at 100r/min for 30min to obtain the product containing WO 4 2- A metal salt solution of (a).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing by using liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times by using deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (tungsten-doped bismuth oxychloride material).
Example 11
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 4.75g (0.015 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to obtain bismuth chloride powder (particle size 200 nm).
(2) 0.484g (0.0024 mol) of sodium molybdate is added into 20mL of deionized water and stirred for 30min under the condition of 400r/min to form a mixture containing MoO 4 2- A metal salt solution of (a).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times with deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (molybdenum-doped bismuth oxychloride material).
Example 12
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 4.75g (0.015 mol) of bismuth chloride was ground at room temperature for 30min under anhydrous conditions to obtain bismuth chloride powder (particle size 500 nm).
(2) 2.42g (0.012 mol) of sodium molybdate is added into 20mL of deionized water and stirred for 30min under the condition of 400r/min to form MoO 4 2- The metal salt solution of (2).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times with deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (molybdenum-doped bismuth oxychloride material).
Example 13
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 4.75g (0.015 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to give bismuth chloride powder (particle size 200 nm).
(2) 2.42g (0.012 mol) of sodium molybdate is added into 50mL of deionized water and stirred for 30min under the condition of 400r/min to form a mixture containing MoO 4 2- A metal salt solution of (a).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times with deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (molybdenum-doped bismuth oxychloride material).
Example 14
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 4.75g (0.015 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to give bismuth chloride powder (particle size 200 nm).
(2) Adding 0.368g (0.002 mol) of sodium vanadate into 20mL of deionized water, and stirring for 30min under the condition of 400r/min to form the solution containing VO 4 2- A metal salt solution of (a).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times with deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (vanadium-doped bismuth oxychloride material).
Example 15
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 4.75g (0.015 mol) of bismuth chloride was ground at room temperature for 30min under anhydrous conditions to obtain bismuth chloride powder (particle size 500 nm).
(2) Adding 0.736g (0.004 mol) of sodium vanadate into 20mL of deionized water, and stirring for 30min under the condition of 400r/min to form VO-containing solution 4 2- A metal salt solution of (a).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times with deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (vanadium-doped bismuth oxychloride material).
Example 16
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 4.75g (0.015 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to obtain bismuth chloride powder (particle size 200 nm).
(2) Adding 0.736g (0.004 mol) of sodium vanadate into 50mL of deionized water, and stirring for 30min under the condition of 400r/min to form VO-containing solution 4 2- A metal salt solution of (a).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times with deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (vanadium-doped bismuth oxychloride material).
Example 17
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 1.26g (0.004 mol) of bismuth chloride was ground at room temperature for 60min under anhydrous conditions to obtain bismuth chloride powder (particle size: 200 nm).
(2) 0.368g (0.002 mol) of sodium vanadate is added into 20mL of deionized water and stirred for 30min under the condition of 100r/min to form VO-containing solution 4 2- A metal salt solution of (a).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times with deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (vanadium-doped bismuth oxychloride material).
Example 18
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 1.26g (0.004 mol) of bismuth chloride was ground at room temperature for 30min under anhydrous conditions to obtain bismuth chloride powder (particle size 500 nm).
(2) 0.368g (0.002 mol) of sodium vanadate is added into 20mL of deionized water and stirred for 30min under the condition of 400r/min to form VO-containing solution 4 2- The metal salt solution of (2).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring for 10min at room temperature, separating out a precipitate, freezing by using liquid nitrogen, transferring into a vacuum freeze dryer, drying for 48h under the vacuum condition of-50 ℃, then mixing and washing for 5 times by using deionized water and absolute ethyl alcohol, removing impurities, finally drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (the vanadium-doped bismuth oxychloride material).
Example 19
A preparation method of a high-stability bismuth oxychloride photocatalytic material comprises the following steps:
(1) 1.26g (0.004 mol) of bismuth chloride was ground at room temperature for 30min under anhydrous conditions to obtain bismuth chloride powder (particle size 500 nm).
(2) 0.368g (0.002 mol) of sodium vanadate is added into 20mL of deionized water and stirred for 30min under the condition of 400r/min to form VO-containing solution 4 2- A metal salt solution of (a).
(3) Uniformly spreading bismuth chloride powder at the bottom of a 100mL beaker, quickly pouring a metal salt solution into the bismuth chloride powder, ultrasonically stirring at room temperature for 30min, separating out a precipitate, freezing with liquid nitrogen, transferring into a vacuum freeze dryer, drying at-50 ℃ for 48h under a vacuum condition, mixing and washing with deionized water and absolute ethyl alcohol for 5 times, removing impurities, drying the washed sample in an oven at 60 ℃ for 12h, and grinding to obtain the high-stability bismuth oxychloride photocatalytic material (vanadium-doped bismuth oxychloride material).
The photocatalytic hydrogen production performance of the high-stability bismuth oxychloride photocatalytic materials prepared in example 11 and example 19 is measured, and the result is shown in fig. 8, wherein the f curve in fig. 8 is example 11, and the g curve in fig. 8 is example 19.
As can be seen from fig. 8, the high-stability bismuth oxychloride photocatalytic materials prepared in examples 11 and 19 have very stable hydrogen production performance, and the hydrogen production performance is also very efficient.
Example 1
0.002mol of potassium chloride was dissolved in 20mL of glycerin, and 0.002mol of bismuth nitrate pentahydrate was also dissolved in 20mL of glycerin. Then, the potassium chloride solution was added to the bismuth nitrate pentahydrate solution with constant stirring. The suspension was transferred to a tetrafluoroethylene-lined stainless steel autoclave (50 mL) which was then kept at 160 ℃ for 16h. After the reaction is finished, a BiOCl precipitate is obtained by centrifugation and then is washed by ethanol and deionized water. Finally, the sample is dried in the air at 60 ℃ for 12h to obtain pure flaky bismuth oxychloride.
Example 2
Lithium nitrate and potassium nitrate are mixed in a molar ratio of 53:72 for 60min, and then 0.97g of bismuth nitrate pentahydrate, 0.5g of potassium chloride and 0.33g of sodium tungstate are added to the mixed salt and ball-milled for 3h. The mixed powder was fed into an alumina crucible, annealed at 350 ℃ for 3h and then naturally cooled to ambient temperature. Washing with deionized water and ethanol was repeated 5 times. Finally, the sample is dried in air at 60 ℃ for 12h to obtain the tungsten-doped bismuth oxychloride.
Example 3
An amount of sodium tungstate was dispersed in 50mL of water, designated as solution A, and then 0.5g of PVP (polyvinylpyrrolidone) was dissolved in 50mL of water. After stirring for 15min, 2mL of hydrochloric acid (37% strength by volume) and 2.13g of bismuth nitrate pentahydrate were dissolved in the solution. The resulting solution was designated as solution B. Then, solution A was poured into solution B and stirred for 10min to form a uniform distribution. Subsequently, 80mL of the final solution was transferred to a 100mL autoclave and heated at 180 ℃ for 12h. Then, the solution was cooled to room temperature, and the precipitate was separated, and washed with ethanol and deionized water 5 times. Finally, the sample is dried in air at 60 ℃ for 12h to obtain the tungsten-doped bismuth oxychloride.
The photocatalytic hydrogen production performance of the photocatalytic materials prepared in examples 1 to 3 was measured, and the results are shown in fig. 9, where the h-curve in fig. 9 is an example 1, the i-curve in fig. 2, and the j-curve in fig. 3.
As can be seen from fig. 9, the pure flake bismuth oxychloride obtained in the demonstration example 1 has no photocatalytic activity within 5 hours, and does not produce hydrogen, while the tungsten-doped bismuth oxychloride prepared in the demonstration example 2 by the molten salt method has improved photocatalytic activity within 5 hours, and has a certain hydrogen production capacity from the original absence of hydrogen production activity, but has a little lack of stability. In the demonstration example 3, the hydrogen production performance of the tungsten-doped bismuth oxychloride prepared by a hydrothermal method is greatly improved within 5 hours, and the stability is improved to a certain extent, but compared with the tungsten-doped bismuth oxychloride sample prepared in the example 1, the difference between the hydrogen production rate and the hydrogen production capacity is large, and the reason is the influence of the synthesis temperature on the structure of the bismuth oxychloride in the synthesis process, so that the hydrogen production performance is influenced. Therefore, the method provided by the invention can be used for doping at room temperature and drying under a vacuum freezing condition to further maintain the original structure of BiOCl, so that the BiOCl is not damaged, the doping of the metal elements enables the BiOCl to have hydrogen production performance, and the stable crystal structure enables the hydrogen production stability to be greatly improved.
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (3)
1. The application of the high-stability bismuth oxychloride photocatalytic material in photocatalytic hydrogen production is characterized in that the preparation method of the high-stability bismuth oxychloride photocatalytic material comprises the following steps:
quickly pouring a rare metal salt solution into the bismuth source powder, ultrasonically stirring at room temperature, separating out a precipitate, freezing by using liquid nitrogen, and then carrying out vacuum freeze drying to obtain the high-stability bismuth oxychloride photocatalytic material;
the preparation of the rare metal salt solution specifically comprises the following steps: adding rare metal salt into water, and stirring to obtain a rare metal salt solution;
the rare metal salt comprises one or more of sodium tungstate, sodium metatungstate, sodium vanadate and sodium molybdate;
the preparation of the bismuth source powder specifically comprises the following steps: grinding a bismuth source under an anhydrous condition until the particle size is 200 to 500nm to obtain bismuth source powder;
the bismuth source comprises bismuth chloride;
the mass ratio of the bismuth source powder to the rare metal salt in the rare metal salt solution is 0.9-22.5;
the temperature of the vacuum freeze drying is-52 to-48 ℃, and the time is 45 to 50h.
2. The application of the high-stability bismuth oxychloride photocatalytic material in photocatalytic hydrogen production is characterized in that in the preparation process of the rare metal salt solution, the stirring speed is 100 to 400r/min, and the stirring time is 25 to 35min.
3. The application of the high-stability bismuth oxychloride photocatalytic material in photocatalytic hydrogen production according to claim 1, wherein the time for ultrasonic stirring is 10 to 30min.
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| US10717664B2 (en) * | 2013-08-05 | 2020-07-21 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Photocatalysts based on bismuth oxyhalide, process for their preparation and uses thereof |
| CN103920510A (en) * | 2014-05-06 | 2014-07-16 | 阜阳师范学院 | Preparation method and application of photocatalyst Mn-BiOCl |
| CN108383160B (en) * | 2018-04-11 | 2020-04-07 | 湘潭大学 | Preparation method and application of metal element doped BiOCl nanosheet material |
| CN111617784A (en) * | 2020-06-23 | 2020-09-04 | 盐城工学院 | Preparation method and application of two-dimensional layered bismuth oxychloride-Fe doped modified photocatalytic material |
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