CN109529864B - alpha-Fe2O3/Bi2WO6Shell composite photocatalyst and preparation method thereof - Google Patents
alpha-Fe2O3/Bi2WO6Shell composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910003145 α-Fe2O3 Inorganic materials 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 53
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 44
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 44
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000010304 firing Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 150000001621 bismuth Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- -1 modified bismuth tungstate Chemical class 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 27
- 230000001699 photocatalysis Effects 0.000 description 17
- 238000007146 photocatalysis Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003574 free electron Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 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 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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Abstract
The invention relates to the field of photocatalysts, and provides alpha-Fe for solving the problems of low efficiency, high preparation cost and the like of the existing photocatalyst in use2O3/Bi2WO6Shell composite photocatalyst and a preparation method thereof. The composite photocatalyst takes shell powder as a carrier, and the carrier is connected with nano Bi2WO6And nano alpha-Fe grows in situ on the carrier2O3And alpha-Fe thereof2O3And Bi2WO6The content of (A) is 2.5-3.5 wt% and 23-27.5 wt%, respectively. The preparation method comprises the following steps: 1) the method comprises the following steps of (1) taking shell powder as a carrier, and dispersing the carrier in a dispersing agent; 2) adding bismuth tungstate and an iron source into a dispersing agent, uniformly mixing and then curing to obtain a precursor; 3) firing the precursor to obtain alpha-Fe2O3/Bi2WO6Shell composite photocatalyst. The method has the advantages of wide raw material source, low cost, simple process, easy operation and suitability for large-scale production.
Description
Technical Field
The invention relates to the field of photocatalysts, in particular to alpha-Fe2O3/Bi2WO6Shell composite photocatalyst and a preparation method thereof.
Background
Currently, in the world today, photocatalysis is undoubtedly one of the most promising technologies. The solar energy source is applied to a plurality of aspects, such as obtaining hydrogen energy by photolyzing water, and can effectively solve the problem of sewage treatment in the industry at present. The conventional photocatalyst is TiO2Is a representative metal oxide and sulfide, but the world health organization International cancer research organization has been on 2017, 10 and 27 months2The compound is listed in a 2B carcinogen list, and can only be driven by ultraviolet light accounting for 4% of the solar energy, so that the efficiency is low. China has abundant bismuth element reserves, low price, safety and no toxicity, and has great natural advantages in developing bismuth-based photocatalytic materials. However, Bi alone2WO6The two defects of narrow light absorption range and low light quantum efficiency still exist, the effect of photocatalytic degradation of pollutants is hopeful to be further promoted, the Chinese patent office discloses a preparation method of an iron oxide/bismuth tungstate composite photocatalyst in 2013, 8, month and 14, the invention patent is granted with the publication number of CN102500390B, the conforming catalyst is powder comprising iron oxide and bismuth tungstate, wherein the molar ratio of the iron oxide to the bismuth tungstate is 1: 2-20, and the preparation steps comprise: mixing a nitric acid solution of bismuth nitrate pentahydrate, a sodium hydroxide solution of ammonium tungstate and a soluble iron salt solution, and preparing the iron oxide/bismuth tungstate composite photocatalyst by a hydrothermal method of microwave-assisted heating. The bismuth tungstate is used for replacing the traditional titanium oxide, the cost is saved, and the recombination probability of photoproduction electrons and holes is reduced by introducing stable and nontoxic iron oxide, because the iron oxide and bismuth tungstate double semiconductors have two different energy band structures, the energy band positions are different, so that potential energy difference is generated, namely the iron oxide and bismuth tungstate have a synergistic strengthening effect, and the bismuth tungstate has more excellent photocatalysis performance.
The Chinese patent office also discloses an iron oxide/bismuth tungstate composite photocatalyst as well as a preparation method and application thereof on 21/1/2015, wherein the authorization publication number is CN102824917B, and the iron oxide/bismuth tungstate composite photocatalyst is prepared by soaking and low-temperature roasting technology in Bi2WO6The surface is deposited with 10-30nm Fe2O3And (3) nanoparticles. Compared with the former, the scheme of the invention further improves the appearance and the component ratio, so that the performance of the invention is further improved.
The Chinese patent office also discloses a photocatalyst Fe in 2017, 5 and 31 months2O3-WO3The invention and the patent application of the preparation method thereof use a tungsten source to prepare the tungsten oxide, prepare the ferric oxide on the surface in situ, and compound the tungsten oxide and the ferric oxide at high temperature, thereby improving the preparation efficiency, being green and environment-friendly, but the photocatalysis performance is actually reduced compared with the former two inventions, and the excellent synergy of the iron oxide and the bismuth tungstate is not exerted.
Disclosure of Invention
In order to solve the problems of low efficiency, high preparation cost and the like of the existing photocatalyst in use, the invention provides alpha-Fe2O3/Bi2WO6Shell composite photocatalyst and a preparation method thereof. The composite photocatalyst has the advantages of wide raw material source, low cost and excellent photocatalytic performance, and the prepared composite photocatalyst is more environment-friendly, is beneficial to recovery and avoids secondary pollution caused by the photocatalyst.
In order to achieve the purpose, the invention adopts the following technical scheme.
alpha-Fe2O3/Bi2WO6Shell composite photocatalyst, which takes shell powder as a carrier, and the carrier is connected with nano Bi2WO6And nano alpha-Fe grows in situ on the carrier2O3And alpha-Fe thereof2O3And Bi2WO6The content of (A) is 2.5-3.5 wt% and 23-27.5 wt%, respectively.
The shell comprises CaCO as main ingredient3The photocatalysis reaction can be promoted to be carried out under proper alkaline conditions; the porous structure of the photocatalyst can adsorb and trap pollutants, and improve the photocatalytic efficiency; in addition, the floating shell carrier can improve the utilization rate of the catalyst to sunlight, excite the activity and improve the photodegradation performance to pollutants(ii) a Can solve the application problems of easy agglomeration, difficult recovery and the like of the nano photocatalyst. While alpha-Fe grown in situ2O3And nano Bi2WO6The two can generate excellent synergistic interaction, so that the photocatalytic performance of the integral composite photocatalyst is improved, the raw material sources are very wide, and the cost is extremely low. On the other hand, alpha-Fe2O3The semiconductor is an n-type semiconductor, two carriers in the semiconductor are namely a hole in a valence band and an electron in a conduction band, the semiconductor mainly taking electron conduction is called as an n-type semiconductor, the semiconductor takes conduction mainly through negatively charged electrons, namely free electrons, the free electrons are mainly provided by impurity atoms, the holes are formed by thermal excitation, the more impurities are doped, the higher the concentration of the free electrons is, the stronger the conductivity is, and therefore through a large number of experiments, the alpha-Fe is controlled in the invention2O3The content of (A) is within 2.5-3.5 wt% and the performance is best. Can greatly stimulate the photocatalysis performance of the bismuth tungstate.
Preferably, the composite photocatalyst is powder with the particle size of 10-25 μm.
The photocatalyst is a powder material with high mesh number, and is easier to uniformly disperse when in use.
alpha-Fe2O3/Bi2WO6The preparation method of the shell composite photocatalyst comprises the following steps:
1) grinding shells into shell powder serving as a carrier, and dispersing the carrier in a molten organic dispersing agent;
2) adding bismuth tungstate powder and an iron source into the organic dispersing agent melted in the step 1), uniformly mixing, cooling and solidifying to obtain a precursor;
3) firing the precursor at 450-550 ℃ for 1-3 h to obtain alpha-Fe2O3/Bi2WO6Shell composite photocatalyst.
The whole preparation method is simple, the shell powder carrier and the bismuth tungstate powder are mixed and fixed by virtue of the organic dispersant, and the iron oxide is prepared in situ on the surface of the carrier by burning after mixing and fixing, so that the composite photocatalyst powder with extremely high mesh number can be directly prepared.
Preferably, the particle size of the shell powder in the step 1) is 5-15 μm.
The smaller the particle size of the carrier is, the finer the prepared composite photocatalyst powder is.
Preferably, the bismuth tungstate powder in the step 2) is modified bismuth tungstate powder which is a spiral microsphere with clear layering, and the particle size of the powder is 2.5-3.5 microns.
Compared with the bismuth tungstate powder with a single lamellar or flower-shaped structure, the bismuth tungstate powder with the structure has a larger specific surface area and can generate higher photocatalysis performance.
Preferably, the bismuth tungstate powder is prepared by the following process:
s1) respectively preparing 0.06-0.08 mol/L sodium tungstate solution and 0.12-0.16 mol/L bismuth salt solution, and dropwise adding the sodium tungstate solution into the bismuth salt solution to obtain a pre-solution;
s2) adding sodium dodecyl sulfate into the pre-solution obtained in the step S1), adding 12-15 g of sodium dodecyl sulfate into each liter of pre-solution, uniformly mixing, standing for 3-4 h, drying at 160-185 ℃ for 20-28 h, filtering out precipitates, washing the precipitates to be neutral, and drying to obtain bismuth tungstate powder.
In the process, the bismuth tungstate powder is modified by using the sodium dodecyl sulfate, the absorption of the modified bismuth tungstate powder on ultraviolet light is enhanced, the red shift phenomenon can occur in an absorption spectrum, the absorption threshold is 461nm, so that the absorption range of the bismuth tungstate powder is enlarged in a visible light region, and the photocatalytic performance of the whole composite photocatalyst in the visible light region is greatly improved.
Preferably, the iron source in step 2) is a soluble iron salt.
Soluble ferric salt can be used as an iron source, and the raw material source is wide.
Preferably, the soluble iron salt is ferric nitrate.
When the ferric nitrate is used as an iron source, impurities can be greatly prevented from being doped, and the purity of the whole composite photocatalyst is improved.
Preferably, the organic dispersant of step 2) includes stearic acid, polyethylene glycol and citric acid.
The organic dispersing agent has limited fluidity, can firstly play a role in fixing and bonding the bismuth tungstate powder and the carrier to a certain extent, and can be used for preparing the nano Fe in situ in the follow-up process2O3Plays a great promoting role, and can select the grown nano Fe through the organic dispersant2O3Control is carried out to grow pure nano alpha-Fe2O3Particles, also by changing the kind of organic dispersant or controlling the reaction conditions of the preparation process, to grow alpha-Fe2O3Is mainly doped with a small amount of gamma-Fe2O3The mixed particles of (1).
Preferably, the organic dispersant is polyethylene glycol.
The particle size of the nano iron oxide prepared by using polyethylene glycol as an organic dispersant is small, so that the specific surface area of the whole composite photocatalyst is larger.
The invention has the beneficial effects that:
1) the raw materials of the invention have wide sources and low cost;
2) bismuth tungstate and ferric oxide can play a role in synergy, and on the basis that shell powder is used as a carrier, the composite photocatalyst can still keep higher photocatalytic performance when used under certain alkaline conditions, and the performance is far superior to that of the existing photocatalyst;
3) the shell powder is used as a carrier, so that the problem of waste pollution of shells is solved, the environment is more green, and partial granular pollutants can be intercepted and adsorbed when the pollutants are degraded by photocatalysis, so that the photocatalysis environment is improved, and the photocatalysis efficiency is improved;
4) the photocatalytic performance of the bismuth tungstate powder can be further improved by modifying the bismuth tungstate powder;
5) the preparation process is simple, easy to operate and suitable for large-scale production.
Drawings
FIG. 1 is an EDS inspection of bismuth tungstate powder prepared in example;
FIG. 2 is an SEM photograph of bismuth tungstate powder prepared in example.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only examples of a part of the present invention, and not all examples. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or commonly used in the art; unless otherwise specified, the methods used in the examples of the present invention are conventional methods that can be implemented by those skilled in the art.
Examples 1 to 6
Preparing bismuth tungstate powder:
s1) respectively preparing 0.06-0.08 mol/L sodium tungstate solution and 0.12-0.16 mol/L bismuth salt solution, and dropwise adding the sodium tungstate solution into the bismuth salt solution to obtain a pre-solution;
s2) adding sodium dodecyl sulfate into the pre-solution obtained in the step S1), adding 12-15 g of sodium dodecyl sulfate into each liter of pre-solution, uniformly mixing, standing for 3-4 h, drying at 160-185 ℃ for 20-28 h, filtering out precipitates, washing the precipitates to be neutral, and drying to obtain bismuth tungstate powder.
The specific preparation parameters are shown in table 1 below.
TABLE 1 specific preparation parameters of bismuth tungstate powder
The bismuth tungstate powders prepared in examples 1 to 6 were detected and characterized, wherein the EDS of the bismuth tungstate powder prepared in example 6 is shown in fig. 1 of the accompanying drawings, the SEM is shown in fig. 2 of the accompanying drawings, and S1 and S2 in fig. 2 are SEM images with different magnifications. .
The particle size of the bismuth tungstate powder prepared in examples 1 to 6 was found to be 2.5 to 3.5 μm.
Examples 7 to 12
Preparation of alpha-Fe Using the bismuth tungstate powders obtained in examples 1 to 62O3/Bi2WO6The shell composite photocatalyst comprises the following specific steps:
1) grinding and sieving shells to screen out shell powder with the particle size of 5-15 mu m, taking the shell powder as a carrier, and dispersing the carrier in a molten organic dispersing agent;
2) adding bismuth tungstate powder and an iron source into the organic dispersing agent melted in the step 1), uniformly mixing the bismuth tungstate powder and the iron source, and then cooling and solidifying the mixture by water to obtain a precursor;
3) firing the precursor at 450-550 ℃ for 1-3 h to obtain alpha-Fe2O3/Bi2WO6Shell composite photocatalyst.
The specific parameters during the preparation are shown in table 2 below.
TABLE 2 alpha-Fe2O3/Bi2WO6Specific parameters for preparing shell composite photocatalyst
For the produced alpha-Fe2O3/Bi2WO6Detecting a shell composite photocatalyst, wherein the alpha-Fe2O3And Bi2WO6The content of (a) is within the range of 2.5-3.5 wt% and 23-27.5 wt%, respectively, and the particle size is within the range of 10-25 μm. Also, examples 7 and 9 were examined, among which examples7 also contains 0.03 +/-0.01 wt% of gamma-Fe2O3Example 9 contains 0.15. + -. 0.01 wt% of gamma-Fe2O3。γ-Fe2O3Under the action of an external magnetic field, magnetism can be generated, and the recovery of the composite photocatalyst is facilitated.
For the alpha-Fe prepared in examples 7 to 122O3/Bi2WO6Performing performance detection on the shell composite photocatalyst, preparing a plurality of 30mg/L rhodamine B solutions, and adding the alpha-Fe prepared in the embodiments 7-12 according to the proportion of adding 2g of the composite photocatalyst into each liter of the rhodamine B solutions2O3/Bi2WO6The shell composite photocatalyst is characterized in that the remaining content of rhodamine B in a solution is detected after the rhodamine B is adsorbed for 60min in a darkroom and irradiated for 60min by a xenon lamp respectively, through detection, the remaining content of rhodamine B in all xenon lamp irradiation tests is lower than 3mg/L, namely the removal rate is higher than 90%, and the remaining rhodamine B is higher than 27mg/L under the darkroom adsorption condition, namely the removal rate is lower than 10%, so that the alpha-Fe composite photocatalyst can be proved to be alpha-Fe composite photocatalyst2O3/Bi2WO6The shell composite photocatalyst has excellent photocatalytic effect.
Claims (9)
1. alpha-Fe2O3/Bi2WO6The shell composite photocatalyst is characterized in that shell powder is used as a carrier, and Bi is connected to the carrier2WO6And nano alpha-Fe grows in situ on the carrier2O3And alpha-Fe thereof2O3And Bi2WO6The content of (A) is 2.5-3.5 wt% and 23-27.5 wt%, respectively;
the alpha-Fe2O3/Bi2WO6The preparation method of the shell composite photocatalyst comprises the following steps:
1) grinding shells into shell powder serving as a carrier, and dispersing the carrier in a molten organic dispersing agent; the organic dispersant comprises stearic acid, polyethylene glycol or citric acid;
2) adding bismuth tungstate powder and an iron source into the organic dispersing agent melted in the step 1), uniformly mixing, cooling and solidifying to obtain a precursor;
3) firing the precursor at 450-550 ℃ for 1-3 h to obtain alpha-Fe2O3/Bi2WO6Shell composite photocatalyst.
2. alpha-Fe according to claim 12O3/Bi2WO6The shell composite photocatalyst is characterized by being powder with the particle size of 10-25 mu m.
3. alpha-Fe as defined in claim 1 or 22O3/Bi2WO6The preparation method of the shell composite photocatalyst is characterized by comprising the following steps:
1) grinding shells into shell powder serving as a carrier, and dispersing the carrier in a molten organic dispersing agent; the organic dispersant comprises stearic acid, polyethylene glycol or citric acid;
2) adding bismuth tungstate powder and an iron source into the organic dispersing agent melted in the step 1), uniformly mixing, cooling and solidifying to obtain a precursor;
3) firing the precursor at 450-550 ℃ for 1-3 h to obtain alpha-Fe2O3/Bi2WO6Shell composite photocatalyst.
4. alpha-Fe according to claim 32O3/Bi2WO6The preparation method of the shell composite photocatalyst is characterized in that the particle size of the shell powder in the step 1) is 5-15 microns.
5. alpha-Fe according to claim 32O3/Bi2WO6The preparation method of the shell composite photocatalyst is characterized in that the bismuth tungstate powder in the step 2) is modified bismuth tungstate powder which is a spiral microsphere with clear layering, and the particle size of the powder is 2.5-3.5 microns.
6. alpha-Fe according to claim 52O3/Bi2WO6The preparation method of the shell composite photocatalyst is characterized in that the bismuth tungstate powder is prepared by the following processes:
s1) respectively preparing 0.06-0.08 mol/L sodium tungstate solution and 0.12-0.16 mol/L bismuth salt solution, and dropwise adding the sodium tungstate solution into the bismuth salt solution to obtain a pre-solution;
s2) adding sodium dodecyl sulfate into the pre-solution obtained in the step S1), adding 12-15 g of sodium dodecyl sulfate into each liter of pre-solution, uniformly mixing, standing for 3-4 h, drying at 160-185 ℃ for 20-28 h, filtering out precipitates, washing the precipitates to be neutral, and drying to obtain bismuth tungstate powder.
7. alpha-Fe according to claim 32O3/Bi2WO6The preparation method of the shell composite photocatalyst is characterized in that the iron source in the step 2) is soluble iron salt.
8. alpha-Fe according to claim 72O3/Bi2WO6The preparation method of the shell composite photocatalyst is characterized in that the soluble ferric salt is ferric nitrate.
9. alpha-Fe according to claim 32O3/Bi2WO6The preparation method of the shell composite photocatalyst is characterized in that the organic dispersing agent is preferably polyethylene glycol.
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