CN115672325B - FeB/CST composite material and preparation method and application thereof - Google Patents
FeB/CST composite material and preparation method and application thereof Download PDFInfo
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- CN115672325B CN115672325B CN202211213640.1A CN202211213640A CN115672325B CN 115672325 B CN115672325 B CN 115672325B CN 202211213640 A CN202211213640 A CN 202211213640A CN 115672325 B CN115672325 B CN 115672325B
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229920000426 Microplastic Polymers 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims description 34
- 239000012298 atmosphere Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 15
- 229910052796 boron Inorganic materials 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- -1 iron ion Chemical class 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 8
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 6
- 230000002195 synergetic effect Effects 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 230000031700 light absorption Effects 0.000 abstract description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 8
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 5
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 46
- 239000000243 solution Substances 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 27
- 238000003756 stirring Methods 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 239000012043 crude product Substances 0.000 description 17
- 239000012535 impurity Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 229910021642 ultra pure water Inorganic materials 0.000 description 14
- 239000012498 ultrapure water Substances 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 239000004809 Teflon Substances 0.000 description 7
- 229920006362 Teflon® Polymers 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000010951 particle size reduction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007557 optical granulometry Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention belongs to the technical field of environmental and energy catalysis, and particularly relates to a FeB/CST composite material, and a preparation method and application thereof. The composite material regulates and controls TiO through iron boride FeB 2 The semiconductor structure of (2) improves the traditional TiO 2 The defects of low utilization efficiency of visible light and easy recombination of photo-generated carriers are overcome, the utilization efficiency of photo-generated electrons and holes of the photo-catalytic material is improved, the quantum efficiency of photo-catalytic degradation and hydrogen production is increased, and the traditional TiO is improved 2 The light absorption performance and the pollutant adsorption performance of the material cooperate with water to produce hydrogen while degrading the microplastic by photocatalysis, thereby realizing the pollution control and water resource utilization of the microplastic in water environment.
Description
Technical Field
The invention belongs to the technical field of environmental and energy catalytic utilization. More particularly, relates to a FeB/CST composite material, a preparation method and application thereof.
Background
In recent years, with the acceleration of the progress of industrialization, urbanization and agricultural modernization, the demands for plastic products are increasing, and plastics enter water environment due to mass use or improper treatment and are formed into micro plastics through the processes of crushing, aging and the like. The microplastic as a new environmental pollutant becomes a research focus for environmental pollution control and water environment improvement in China. At present, various micro-plastic pollution treatment technologies such as biodegradation, thermal cracking or photocatalytic degradation and the like are developed aiming at the characteristics of high stability and oxidation resistance of micro-plastics, wherein the photocatalytic degradation technology is green and free of secondary pollution, and energy sources mainly come from solar energy and the like, so that the micro-plastic pollution treatment technology is paid attention to by researchers.
In addition, hydrogen is widely applied as a clean energy source in the fields of agriculture, pharmacy, chemical industry and the like, and photocatalytic hydrogen production is a very promising technology and is widely paid attention to by researchers. In the photocatalytic hydrogen production process, protons in water combine with photogenerated electrons, but a sacrificial agent is typically required to consume the photogenerated holes to facilitate separation of carriers. Chinese patent application CN114832836A discloses an amphiphilic CoP/g-C for the synergistic hydrogen production of degraded microplastic 3 N 4 A material and a method for preparing the same, wherein the material is prepared by mixing g-C 3 N 4 Mixing with ZIF-67 nanosheets in a composite solvent, and phosphating to obtain amphiphilic CoP/g-C 3 N 4 A material; the material can obtain amphiphilic CoP/g-C with different hydrophobicity after being treated by different solvents 3 N 4 The material is controlled to be combined with H in the process of producing hydrogen cooperatively by photocatalytic degradation of microplastic + And the micro plastic, so that the micro plastic shows different photocatalysis performance. Therefore, the micro-plastics can be degraded by utilizing the photocatalyst, and the pollution of the micro-plastics can be effectively reduced and the water resource utilization can be realized at the same time by utilizing the synergistic photocatalytic water splitting hydrogen production, but the related researches are still less at present.
TiO 2 As a typical photocatalyst, the photocatalyst can realize the efficient separation of photon-generated carriers under the irradiation of ultraviolet rays, and is widely studied in photocatalytic pollutant degradation and water splitting hydrogen production. However, tiO 2 The forbidden bandwidth (3.2 eV) of the light-sensitive fluorescent material is caused to respond only under ultraviolet light, and the photo-generated carriers are easy to be compounded. Chinese patent application CN112958134A discloses an Ag-modified N-doped porous carbon-loaded TiO 2 Composite material, in which TiO 2 Can decompose toluene into carbon dioxide and water under mild condition, and the metallic silver has a large light absorption section in the visible light region, has surface plasmon resonance effect, and is doped on a photocatalyst to enable TiO to be 2 The light absorption range moves towards the long wave direction, so that the light absorption capacity of the material and the separation efficiency of photo-generated electron holes in the photocatalysis process are improved. However, noble metal loading, while effective in accelerating electron-hole separation and surface electron transport, is scarce and costly, which prevents its large-scale industrial application.
Therefore, a photocatalysis composite material with low cost and visible light response is sought, and the rapid separation of photocatalysis electron-hole is accelerated, so that the high-efficiency microplastic conversion and photocatalysis water decomposition hydrogen production are realized, and the method has very important significance for microplastic pollution control and water resource utilization.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings of the existing technology for relieving the pollution of microplastic, and provides a preparation method of a FeB/CST composite material for cooperatively producing hydrogen by photocatalytic degradation of microplastic.
The invention further aims to provide a FeB/CST composite material for the synergistic hydrogen production of the photocatalytic degradation microplastic.
The invention also aims to provide the application of the FeB/CST composite material in the synergistic hydrogen production of the catalytic degradation microplastic.
The above object of the present invention is achieved by the following technical scheme:
a preparation method of a FeB/CST composite material comprises the following steps:
immersing CST in an iron ion solution for 8-15 h to obtain a suspension, drying the obtained suspension, calcining at 150-250 ℃ to fully react to obtain a precursor, dispersing the obtained precursor in water, adding a boron reducing agent/alkaline reagent solution under the conditions of inert atmosphere protection and 0-5 ℃, stirring at a speed of 400-600 rpm until no bubbles are generated in a reaction system, and performing post-treatment to obtain the FeB/CST composite material.
Wherein CST is TiO having a core-shell structure 2 。
Preferably, the ferric ion solution is prepared from ferric salt, wherein the ferric salt is selected from any one of ferrous sulfate, ferric nitrate and ferric chloride.
Preferably, the boron reducing agent is selected from one of sodium borohydride, potassium borohydride and ammonia borane.
Preferably, the mass ratio of the iron ions to the CST is 0.01-0.1: 1.
preferably, the molar ratio of boron element to iron ion in the boron reducing agent is 4-9: 1.
more preferably, the molar ratio of boron element and iron ion in the boron reducing agent is 8:1.
preferably, the concentration of the boron reducing agent after being added is 1-3 mol/L.
Preferably, the concentration of the alkaline agent after addition is 0.1 to 0.3mol/L.
Preferably, the alkaline agent is selected from sodium hydroxide or potassium hydroxide.
Preferably, the time of the impregnation is 12 hours.
Preferably, the temperature of the calcination is 200 ℃.
Preferably, the time for obtaining the precursor by the full reaction is 1-3 h.
More preferably, the time for the sufficient reaction to obtain the precursor is 2 hours.
Further, the post-treatment includes centrifugation and washing.
Further, the preparation method of the CST specifically comprises the following steps:
fully mixing an organic reagent and a titanium source under the protection of room temperature and inert atmosphere, carrying out solvothermal reaction to obtain a precursor, cooling, post-treating and roasting to obtain the CST.
Preferably, the titanium source is selected from one of titanyl sulfate, butyl titanate and titanium tetrachloride.
Further, the temperature of the solvothermal reaction is 100-130 ℃; preferably, the solvothermal reaction temperature is 110 ℃.
Further, the solvothermal reaction time is 24-72 h; preferably, the solvothermal reaction time is 48 hours.
Further, the roasting temperature is 500-550 ℃; preferably, the firing temperature is 550 ℃.
Further, the roasting time is 2-4 hours; preferably, the calcination time is 3 hours.
Preferably, the organic reagent is glycerol, ethanol, and anhydrous diethyl ether.
Preferably, the volume ratio of the glycerol, the ethanol and the anhydrous diethyl ether is 1:1.5 to 2:0.8 to 1.
In particular, the post-treatment operations include centrifugation, washing and drying.
Further, the inert atmosphere gases include, but are not limited to, nitrogen, helium, argon, and neon.
The invention also provides the FeB/CST composite material prepared by the preparation method.
Wherein, the combination of the iron ions and the CST is enhanced by a calcining mode, and then a boron reducing agent is added, and the boron reducing agent is used as a reducing agent of an iron source while introducing boron element to promote the reduction of iron to form FeB, and the CST is modified together to form the FeB/CST composite material.
Further, the FeB is distributed on the surface of the core-shell structure of the CST in the form of amorphous alloy.
In addition, the invention also provides application of the FeB/CST composite material in catalyzing and degrading microplastic to cooperatively produce hydrogen.
The invention has the following beneficial effects:
1. the FeB/CST composite material obtained by the invention regulates and controls TiO through iron boride FeB 2 Is improved in TiO 2 The utilization efficiency of visible light is low and the photo-generated carriers are easy to be compounded.
2. The FeB/CST composite material obtained by the invention is in a core-shell structure, and FeB is distributed on the surface of CST in the form of amorphous alloy, thereby improving the traditional TiO 2 The light absorption properties of the material and the adsorption properties of the material to contaminants.
3. The FeB/CST photocatalysis composite material disclosed by the invention can realize the water resource utilization and the pollution control of the microplastic in the water environment by cooperatively decomposing and producing hydrogen while the microplastic is subjected to photocatalysis degradation, and the photon-hole utilization efficiency of the photocatalysis material is improved, and the quantum efficiency of the photocatalysis degradation and hydrogen production is increased.
4. The FeB/CST composite material obtained by the invention adopts iron boride FeB composite with low price, thereby solving the problem of higher cost caused by the traditional noble metal load.
Drawings
FIG. 1 is a scanning electron microscope image of a FeB/CST (7 FBT) composite material according to example 3 of the present invention.
FIG. 2 is a transmission electron microscope image of FeB/CST (7 FBT) composite material in example 3 of the present invention.
FIG. 3 is an X-ray diffraction pattern of FeB/CST composites of examples 1 to 4, CST of comparative example 1, and FeB of comparative example 2 of the present invention.
FIG. 4 is a graph showing photocurrent response of FeB/CST composites of examples 1 to 4 of the present invention and CST of comparative example 1.
FIG. 5 is a graph showing the diffuse reflection of UV-visible light for FeB/CST composites of examples 1-4 and CST of comparative example 1 of the present invention.
FIG. 6 is an activity graph of the photocatalytic degradation of polystyrene microplastic in a body of water for the FeB/CST composites of examples 1-4, the CST of comparative example 1, and the FeB of comparative example 2.
FIG. 7 is a graph showing photocatalytic hydrogen production activities of FeB/CST composites in examples 1 to 4, CST in comparative example 1, and FeB in comparative example 2.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1 preparation method of FeB/CST composite Material
Preparation of s1.cst: mixing 10mL of glycerol and 20mL of ethanol under the protection of room temperature and inert atmosphere, stirring for 10min, slowly dripping 1mL of titanyl sulfate, continuously stirring for 10min, dripping 10mL of anhydrous diethyl ether, continuously stirring for 30min, transferring the solution into a 50mL Teflon lining stainless steel kettle, performing solvothermal reaction for 48h in a 110 ℃ oven, cooling to room temperature, centrifuging the mixed solution in the kettle, washing with ultrapure water and ethanol for several times, removing unreacted raw materials and generated impurities, drying at 60 ℃ for 12h to obtain a precursor, and roasting the obtained precursor in a muffle furnace at 550 ℃ for 3h to obtain TiO with a core-shell structure 2 It was named CST;
s2, preparation of FeB/CST composite material: 200mg of the CST obtained in step S1 was taken through 126uL of FeSO 4 Dipping the solution (0.85 mol/L) for 12H, then drying the obtained suspension at 60 ℃, calcining the dried suspension in a muffle furnace at 200 ℃ for 2H to obtain a precursor, and dispersing the precursor in 10mL of H 2 In the O, the total number of the components is equal to the total number of the components,under the protection of inert atmosphere and at the temperature of 4 ℃, 428.4uL NaBH is added dropwise 4 And (2 mol/L)/NaOH (0.2 mol/L) mixed solution is stirred at the speed of 500rpm until no bubbles are generated in the solution, so as to obtain a crude product, and finally, the obtained crude product is centrifuged and washed for a plurality of times by ultrapure water and ethanol, unreacted raw materials and generated impurities are removed, so that the FeB/CST composite material is obtained, and the FeB/CST composite material is named as 3FBT.
Example 2 preparation method of FeB/CST composite Material
Preparation of s1.cst: mixing 10mL of glycerol and 20mL of ethanol under the protection of room temperature and inert atmosphere, stirring for 10min, slowly dripping 1mL of titanyl sulfate, continuously stirring for 10min, dripping 10mL of anhydrous diethyl ether, continuously stirring for 30min, transferring the solution into a 50mL Teflon lining stainless steel kettle, performing solvothermal reaction for 48h in a 110 ℃ oven, cooling to room temperature, centrifuging the mixed solution in the kettle, washing with ultrapure water and ethanol for several times, removing unreacted raw materials and generated impurities, drying at 60 ℃ for 12h to obtain a precursor, and roasting the obtained precursor in a muffle furnace at 550 ℃ for 3h to obtain TiO with a core-shell structure 2 It was named CST;
s2, preparation of FeB/CST composite material: 200mg of the CST obtained in step S1 was taken through 210uL of FeSO 4 Dipping the solution (0.85 mol/L) for 12H, then drying the obtained suspension at 60 ℃, calcining the dried suspension in a muffle furnace at 200 ℃ for 2H to obtain a precursor, and dispersing the precursor in 10mL of H 2 In O, under the protection of inert atmosphere and at the temperature of 4 ℃, 714uL NaBH is added dropwise 4 And (2 mol/L)/NaOH (0.2 mol/L) mixed solution is stirred at the speed of 500rpm until no bubbles are generated in the solution, so as to obtain a crude product, and finally, the obtained crude product is centrifuged and washed for a plurality of times by ultrapure water and ethanol, unreacted raw materials and generated impurities are removed, so that the FeB/CST composite material is obtained, and the FeB/CST composite material is named as 5FBT.
Example 3 preparation method of FeB/CST composite Material
Preparation of s1.cst: mixing 10mL of glycerol and 20mL of ethanol at room temperature under the protection of inert atmosphere, stirring for 10min, and slowly dropwise adding 1mL of titanyl sulfateContinuously stirring for 10min, dropwise adding 10mL of anhydrous diethyl ether, continuously stirring for 30min, transferring the solution into a 50mL Teflon lining stainless steel kettle, hydrothermal treating in a 110 ℃ oven for 48h, cooling to room temperature, centrifuging the mixed solution in the kettle, washing with ultrapure water and ethanol for several times, removing unreacted raw materials and generated impurities, drying at 60 ℃ for 12h to obtain a precursor, and roasting the obtained precursor in a muffle furnace at 550 ℃ for 3h to obtain the TiO with a core-shell structure 2 It was named CST;
s2, preparation of FeB/CST composite material: 200mg of CST obtained in step S1 was taken through 294.1uL of FeSO 4 Dipping the solution (0.85 mol/L) for 12H, then drying the obtained suspension at 60 ℃, calcining the dried suspension in a muffle furnace at 200 ℃ for 2H to obtain a precursor, and dispersing the precursor in 10mL of H 2 In O, 1000uL NaBH is added dropwise under the protection of inert atmosphere and at the temperature of 4 DEG C 4 And (2 mol/L)/NaOH (0.2 mol/L) mixed solution is stirred at the speed of 500rpm until no bubbles are generated in the solution, so as to obtain a crude product, and finally, the obtained crude product is centrifuged and washed for a plurality of times by ultrapure water and ethanol, unreacted raw materials and generated impurities are removed, so that the FeB/CST composite material is obtained, and the FeB/CST composite material is named as 7FBT.
Example 4 preparation method of FeB/CST composite Material
Preparation of s1.cst: mixing 10mL of glycerol and 20mL of ethanol under the protection of room temperature and inert atmosphere, stirring for 10min, slowly dripping 1mL of titanyl sulfate, continuously stirring for 10min, dripping 10mL of anhydrous diethyl ether, continuously stirring for 30min, transferring the solution into a 50mL Teflon lining stainless steel kettle, hydrothermal for 48h in a 110 ℃ oven, centrifuging the mixed solution in the kettle after cooling to room temperature, washing with ultrapure water and ethanol for several times, removing unreacted raw materials and generated impurities, drying at 60 ℃ for 12h to obtain a precursor, and roasting the obtained precursor in a muffle furnace at 550 ℃ for 3h to obtain the TiO with a core-shell structure 2 It was named CST;
s2, preparation of FeB/CST composite material: 200mg of CST obtained in step S1 were taken through 378.2uL FeSO 4 Solution (0)85 mol/L) is immersed for 12H, then the obtained suspension is dried at 60 ℃, and is calcined for 2H at 200 ℃ in a muffle furnace after the drying is finished to obtain a precursor, and the obtained precursor is dispersed in 10mL of H 2 In O, under the protection of inert atmosphere and at the temperature of 4 ℃, 1285.7uL NaBH is added dropwise 4 And (2 mol/L)/NaOH (0.2 mol/L) mixed solution is stirred at the speed of 500rpm until no bubbles are generated in the solution, so as to obtain a crude product, and finally, the obtained crude product is centrifuged and washed for a plurality of times by ultrapure water and ethanol, unreacted raw materials and generated impurities are removed, so that the FeB/CST composite material is obtained, and the FeB/CST composite material is named as 9FBT.
Example 5 preparation method of FeB/CST composite Material
Preparation of s1.cst: mixing 10mL of glycerol and 20mL of ethanol under the protection of room temperature and inert atmosphere, stirring for 10min, slowly dripping 1mL of titanyl sulfate, continuously stirring for 10min, dripping 10mL of anhydrous diethyl ether, continuously stirring for 30min, transferring the solution into a 50mL Teflon lining stainless steel kettle, hydrothermal for 48h in a 110 ℃ oven, centrifuging the mixed solution in the kettle after cooling to room temperature, washing with ultrapure water and ethanol for several times, removing unreacted raw materials and generated impurities, drying at 60 ℃ for 12h to obtain a precursor, and roasting the obtained precursor in a muffle furnace at 550 ℃ for 3h to obtain the TiO with a core-shell structure 2 It was named CST;
s2, preparation of FeB/CST composite material: 200mg of CST obtained in step S1 was taken through 294.1uL of FeSO 4 Dipping the solution (0.85 mol/L) for 15H, then drying the obtained suspension at 60 ℃, calcining the dried suspension in a muffle furnace at 150 ℃ for 3H to obtain a precursor, and dispersing the obtained precursor in 10mL of H 2 In O, 1000uL NaBH is added dropwise under the protection of inert atmosphere and at 5 DEG C 4 And (2 mol/L)/NaOH (0.2 mol/L) mixing solution and stirring at the speed of 500rpm until no bubble is generated in the solution to obtain a crude product, centrifuging the obtained crude product, washing the crude product for a plurality of times by ultrapure water and ethanol, and removing unreacted raw materials and generated impurities to obtain the FeB/CST composite material.
Example 6 preparation method of FeB/CST composite Material
Preparation of s1.cst: mixing 10mL of glycerol and 20mL of ethanol under the protection of room temperature and inert atmosphere, stirring for 10min, slowly dripping 1mL of titanyl sulfate, continuously stirring for 10min, dripping 10mL of anhydrous diethyl ether, continuously stirring for 30min, transferring the solution into a 50mL Teflon lining stainless steel kettle, hydrothermal for 48h in a 110 ℃ oven, centrifuging the mixed solution in the kettle after cooling to room temperature, washing with ultrapure water and ethanol for several times, removing unreacted raw materials and generated impurities, drying at 60 ℃ for 12h to obtain a precursor, and roasting the obtained precursor in a muffle furnace at 550 ℃ for 3h to obtain the TiO with a core-shell structure 2 It was named CST;
s2, preparation of FeB/CST composite material: 200mg of CST obtained in step S1 was taken through 294.1uL of FeSO 4 Dipping the solution (0.85 mol/L) for 8H, then drying the obtained suspension at 60 ℃, calcining the dried suspension in a muffle furnace at 250 ℃ for 1H to obtain a precursor, and dispersing the precursor in 10mL of H 2 In O, 1000uL NaBH is added dropwise under the protection of inert atmosphere and at 0 DEG C 4 And (2 mol/L)/NaOH (0.2 mol/L) mixing solution and stirring at the speed of 500rpm until no bubble is generated in the solution to obtain a crude product, centrifuging the obtained crude product, washing the crude product for a plurality of times by ultrapure water and ethanol, and removing unreacted raw materials and generated impurities to obtain the FeB/CST composite material.
Comparative example 1A preparation method of CST
Preparation of CST: mixing 10mL of glycerol and 20mL of ethanol under the protection of room temperature and inert atmosphere, stirring for 10min, slowly dripping 1mL of titanyl sulfate, continuously stirring for 10min, dripping 10mL of anhydrous diethyl ether, continuously stirring for 30min, transferring the solution into a 50mL Teflon lining stainless steel kettle, hydrothermal for 48h in a 110 ℃ oven, centrifuging the mixed solution in the kettle after cooling to room temperature, washing with ultrapure water and ethanol for several times, removing unreacted raw materials and generated impurities, drying at 60 ℃ for 12h to obtain a precursor, and roasting the obtained precursor in a muffle furnace at 550 ℃ for 3h to obtain the TiO with a core-shell structure 2 This was designated CST.
Comparative example 2 preparation method of FeB
Preparation of FeB: at 4 ℃ under the protection of inert atmosphere to FeSO 4 NaBH was added dropwise to the solution (0.85 mol/L) 4 (2 mol/L)/NaOH (0.2 mol/L) and stirring at 500rpm until no bubbles were generated in the solution to obtain a crude product, wherein NaBH in the solution was added dropwise 4 With FeSO 4 The mass ratio of Fe substances in the solution is 8: and 1, finally centrifuging the obtained crude product, washing the crude product for a plurality of times by ultrapure water and ethanol, and removing unreacted raw materials and generated impurities to obtain the amorphous alloy FeB.
Experimental example characterization and Performance test of FeB/CST composite, CST and FeB
Characterization and micro plastic catalytic degradation test were performed on the final products prepared in examples 1 to 4 and comparative examples 1 to 2.
(1) Scanning electron microscope and transmission electron microscope observation
The scanning electron microscope image of the FeB/CST (7 FBT) composite obtained in example 3 was measured, and the result is shown in FIG. 1, wherein 7FBT shows a remarkable core-shell structure. The scanning electron micrographs of example 1, example 2 and examples 4 to 6 are substantially identical to the results of example 3.
The transmission electron microscopy image of the FeB/CST (7 FBT) composite obtained in example 3 was measured, and the result was that the FeB was uniformly distributed on the surface of the CST and in an amorphous structure as shown in FIG. 2. The transmission electron micrographs of example 1, example 2 and examples 4 to 6 are substantially identical to the results of example 3.
(2) X-ray diffraction measurement
The X-ray diffraction patterns of FeB/CST composites of examples 1 to 4, CST of comparative example 1 and FeB of comparative example 2 were measured, and the results are shown in FIG. 3, in which FeB was represented as amorphous structure peaks, and TiO in the CST and FeB/CST composites of different proportions 2 The FeB/CST composite material shows an anatase crystal structure, and along with the increase of the Fe content, the FeB/CST composite material shows a weak Fe structure. The X-ray diffraction patterns of example 5 and example 6 are substantially identical to the results of example 3.
(3) Photocurrent response determination
The photocurrent response graphs of the FeB/CST composite materials of examples 1 to 4 and the CST of comparative example 1 were measured, and the results are shown in fig. 4, in which the photocurrent of the FeB/CST composite material was significantly enhanced compared to the CST, and the photocurrent was gradually enhanced with increasing FeB content (3 FBT to 7 FBT), and the electron density was correspondingly improved, indicating that the FeB-modified FeB/CST has superior light capturing ability and photoelectron-hole separation performance. The photocurrent response measurement results of example 5 and example 6 were substantially identical to those of example 3.
(4) Ultraviolet-visible diffuse reflectance measurement
The ultraviolet-visible diffuse reflection patterns of the FeB/CST composite materials in examples 1 to 4 and the CST in comparative example 1 were measured, and the results are shown in FIG. 5, wherein the light absorption range is red shifted from the ultraviolet region to the visible region with the increase of the Fe content, and the absorbance is obviously improved, which indicates that FeB significantly improves the light absorption range of CST and the light absorption capacity. The results of the ultraviolet-visible diffuse reflectance measurements of example 5 and example 6 were substantially identical to those of example 3.
(5) Experimental method for simulating photocatalytic micro-plastic wastewater degradation and co-production of hydrogen
At room temperature, polystyrene microplastic (having a particle size of about 200 um) was added to 30mL of water and mixed with the FeB/CST composite materials of examples 1 to 4, the CST of comparative example 1 and the FeB of comparative example 2, respectively, wherein the amount of polystyrene microplastic was 30mg and the amount of photocatalyst was 50mg. The resulting mixed solution was reacted under light having a wavelength of 365nm for 12 hours. By testing H in the gaseous product with a gas chromatograph 2 The content is as follows; and observing the particle size of the reacted polystyrene micro-plastic by an inverted fluorescence microscope. Each set of experiments was set up with 3 replicates, no catalyst was added to the blank (light only), and the other experimental conditions were unchanged.
The activity patterns of the FeB/CST composite materials in examples 1 to 4, the CST in comparative example 1 and the FeB in comparative example 2 for photocatalytic degradation of polystyrene in water are measured, and the results are shown in FIG. 6, wherein the particle size reduction rate of the microplastic is used as a photocatalyst to the degradation index of the microplastic, and when no photocatalyst is added, the particle size reduction rate of the microplastic is not greatly changed with the time under the illumination condition (photoanalysis); in the experimental group with added CST and FeB, the particle size reduction rate of the microplastic is 53% and 65%, the promotion effect of the FeB/CST composite materials with different proportions on the particle size reduction of the polystyrene microplastic is more obvious, and the particle size reduction rate of the polystyrene is increased along with the increase of the Fe content, wherein under the action of 7FBT, the particle size reduction rate is as high as 92.3%. This indicates that the FeB/CST composite material is effective in promoting the generation of reactive oxygen species to oxidize the microplastic. The results of the microplastic degradation assays of example 5 and example 6 are substantially identical to those of example 3.
The photocatalytic hydrogen production activity patterns of the FeB/CST composite materials in examples 1 to 4, the CST in comparative example 1 and the FeB in comparative example 2 were measured, and the results are shown in FIG. 7, wherein the photocatalytic hydrogen production amounts of the FeB/CST composite materials in different proportions are higher than those of CST and FeB, wherein under the action of 7FBT, the hydrogen production amounts after 12 hours of illumination are up to 103.5umol, which is 1.63 times and 2.25 times the hydrogen production amounts of CST and FeB respectively, and only a trace amount of hydrogen is produced under the same illumination condition (photoanalysis) without adding any catalyst. The FeB/CST composite material has excellent light absorption capacity, promotes the separation of photo-generated electrons and holes, not only effectively promotes the generation of active oxygen so as to oxidize microplastic, but also promotes the combination of photo-generated electrons and proton hydrogen in water, and enhances the photocatalytic hydrogen production. The results of the hydrogen production assays of example 5 and example 6 are substantially identical to those of example 3.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the FeB/CST composite material is characterized by comprising the following steps of:
dipping CST in an iron ion solution for 8-15 h to obtain a suspension, drying the obtained suspension, calcining at 150-250 ℃ to fully react to obtain a precursor, dispersing the obtained precursor in water, adding a boron reducer/alkaline reagent solution under the conditions of inert atmosphere protection and 0-5 ℃ to fully react, and performing post-treatment to obtain the FeB/CST composite material;
wherein CST is TiO having a core-shell structure 2 。
2. The preparation method according to claim 1, wherein the preparation method of the CST specifically comprises the following steps:
fully mixing an organic reagent and a titanium source under the protection of room temperature and inert atmosphere, performing solvothermal reaction to obtain a precursor, cooling, post-treating and roasting to obtain the CST.
3. The preparation method according to claim 1, wherein the mass ratio of the iron ions to CST is 0.01 to 0.1:1.
4. the preparation method according to claim 1, wherein the molar ratio of boron element in the boron reducing agent to iron ions in the solution is 4-9: 1.
5. the production method according to claim 1, wherein the titanium source is selected from any one of titanyl sulfate, butyl titanate, and titanium tetrachloride.
6. The method according to claim 1, wherein the ferric ion solution is prepared from a ferric salt selected from any one of ferrous sulfate, ferric nitrate and ferric chloride.
7. The method according to claim 1, wherein the boron reducing agent is selected from any one of sodium borohydride, potassium borohydride, ammonia borane.
8. The method according to claim 1, wherein the concentration of the boron reducing agent after the addition is 1 to 3mol/L and the concentration of the alkaline agent after the addition is 0.1 to 0.3mol/L.
9. The FeB/CST composite material prepared by the preparation method of any one of claims 1 to 8.
10. The use of the FeB/CST composite material of claim 9 in the synergistic hydrogen production of catalytically degraded microplastic.
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