CN114433065B - Bismuth oxide and bismuth niobate composite material for removing algae in water body, and preparation method and application thereof - Google Patents
Bismuth oxide and bismuth niobate composite material for removing algae in water body, and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 63
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 62
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 241000195493 Cryptophyta Species 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011941 photocatalyst Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 7
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 7
- MBIDWOISWGGCJD-UHFFFAOYSA-N [O].[Bi].[Bi] Chemical compound [O].[Bi].[Bi] MBIDWOISWGGCJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 8
- 238000005215 recombination Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 7
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- 239000011229 interlayer Substances 0.000 abstract description 3
- 230000004298 light response Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- 241000192710 Microcystis aeruginosa Species 0.000 description 10
- 229930002868 chlorophyll a Natural products 0.000 description 10
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
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- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000002353 algacidal effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
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- 230000007613 environmental effect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 241000192700 Cyanobacteria Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004951 kermel Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 108010067094 microcystin Proteins 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
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Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a bismuth oxide and bismuth niobate composite material for removing algae in a water body, and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing sodium hydroxide, sodium bismuthate and water, adding Bi 3 NbO 7 The bismuth oxide and bismuth niobate composite material prepared by the invention can be used for removing harmful algae in water, has better oxygen activation capability and visible light response capability, and in addition, the photo-generated carrier recombination rate of the bismuth oxide and bismuth niobate composite material accelerates interlayer interface charge separation and transfer, so that the bismuth oxide and bismuth niobate composite material has higher photocatalytic activity.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a bismuth oxide and bismuth niobate composite material for removing algae in a water body, and a preparation method and application thereof.
Background
As global climate warms, the problem of eutrophication of water body becomes more serious, and the explosion of harmful algal bloom poses serious threat to aquatic ecosystem, in addition, most of harmful algae, such as algae toxin produced by microcystis aeruginosa, also causes potential safety hazard to water environment. The current methods for controlling harmful algal bloom mainly comprise a physical method, a chemical method, a biological method and the like, such as mechanical salvage, ultrasonic method crushing, biological method algae removal and the like. However, these conventional methods have limited applications due to the corresponding drawbacks. For example, the manual mechanical salvage requires more manpower and material resources in the implementation process, has higher cost and can only be used as an emergency measure when water bloom bursts. The ultrasonic method can lead the content of the algae cells to leak while breaking the cells, and has smaller application range. The biological algae removal method has the advantages of longer treatment period, unstable effect, complex subsequent treatment and serious risk of damaging an ecological system. Therefore, how to effectively control harmful algal bloom is the focus of research in the current environmental field.
In recent years, semiconductor photocatalytic technology has attracted attention because of its advantage of being able to efficiently activate the most green oxidant-molecular oxygen on earth, thereby effectively utilizing solar energy. The photocatalysis technology is applied to the nano photocatalyst, and provides a new idea for solving the problem of harmful algal bloom due to the advantages of high photocatalytic activity, environmental friendliness, low cost, no toxicity and the like. The nano photocatalyst can be activated under light to generate Reactive Oxygen Species (ROS) to damage the cell walls and cell membranes of algae, so that the algae cells are damaged, and in addition, the ROS can also damage the photosynthetic system and the antioxidant system of the algae, further inhibit the activity of the algae and degrade the corresponding microcystin. However, the evolution efficiency of ROS in the photocatalytic reaction process is low at present, which still has a limit when algae are removed from the actual water body in the photocatalytic application. The low evolution efficiency of ROS is mainly due to the fact that, on the one hand, the catalyst is relatively efficient for O 2 In addition to poor specific adsorption of electrons from the catalyst to O 2 Is less efficient, resulting in a lower number of available electrons to participate in oxygen activation. On the other hand, the problems of fast recombination of photo-generated holes and electrons, short service life of photo-generated electrons and the like severely restrict the application in the practical water body. In the enhancement of photocatalytic O 2 In terms of activation, oxygen vacancies play a critical role due to the construction of oxygen vacancies as O 2 Provides coordination unsaturated sites with low valence metals and establishes an effective electron transfer channel, thereby promoting O 2 Is activated by the activation of (a). In addition, the ultra-thin two-dimensional material more easily exposes more oxygen vacancies than the bulk material, which reduces the migration distance of photogenerated electrons, thereby improving the electron transfer capability. But the oxygen vacancies may act as charge recombination centers, in which case, even though the channels are still present, from photocatalyst to O 2 The number of electrons of (2) is also reduced, therebyResulting in poor O 2 Activating. Thus, to achieve efficient photocatalytic O 2 An effective strategy is urgently needed to address the problem of electron shortage.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the preparation method of the bismuth oxide and bismuth niobate composite material for removing algae in water, which has simple process and mild condition, and the prepared bismuth oxide and bismuth niobate composite material has high activity and high stability as a photocatalyst.
The bismuth oxide and bismuth niobate composite material prepared by the preparation method can obviously improve the utilization capacity of a photocatalyst to visible light, accelerate the separation and transfer of interfacial charges between layers and inhibit the recombination of electron hole pairs, thereby greatly improving the photocatalytic capacity and realizing the effective removal of harmful algal bloom.
The invention also aims to provide the application of the bismuth oxide and bismuth niobate composite material in removing algae in a water body, and the bismuth oxide and bismuth niobate composite material can relieve the problem of cyanobacteria bloom in an actual water body.
The aim of the invention is achieved by the following technical scheme.
A preparation method of a bismuth oxide and bismuth niobate composite material for removing algae in a water body comprises the following steps:
mixing sodium hydroxide, sodium bismuthate and water, adding Bi 3 NbO 7 Uniformly stirring, preserving heat at 170-180 ℃ for 5-8 h, centrifuging, washing and centrifuging to obtain a solid, and drying to obtain the bismuth oxide-bismuth niobate composite material, wherein the ratio of the mass portion of sodium hydroxide to the volume portion of sodium bismuthate to the volume portion of water is (2.3-2.4): (2.7-2.8): (50-60) the Bi in parts by weight 3 NbO 7 And sodium bismuthate (4-12): 100.
in the technical scheme, the Bi is prepared 3 NbO 7 The method of (1) is as follows: dripping the first solution into the second solution, stirring at room temperature, and addingAdding benzyl alcohol, regulating pH to 10-15, maintaining at 170-180 deg.c for 18-24 hr, centrifuging, washing the centrifuged solid, and drying to obtain Bi 3 NbO 7 The first solution is a mixture of bismuth nitrate and glacial acetic acid, the second solution is a mixture of niobium oxalate and methanol, the ratio of the mass part of bismuth nitrate to the volume part of glacial acetic acid is (1.4-3): (10-20), the ratio of the mass part of niobium oxalate to the volume part of methanol is (0.5-1.1): (40-80), the unit of the mass part is g, the unit of the volume part is mL, and the ratio of the first solution, the second solution and benzyl alcohol is (1-2) in terms of the volume part: (4-8): (3-6).
In the technical scheme, the drying temperature is 70-80 ℃, and the drying time is 8-10 h.
In the technical scheme, deionized water and absolute ethyl alcohol are adopted for washing.
The bismuth oxide and bismuth niobate composite material obtained by the preparation method.
In the above technical scheme, the bismuth oxide and bismuth niobate composite material comprises: biO (BiO) 2-x Monomers and adhesion to BiO 2-x Bi on monomer surface 3 NbO 7 Particles, 0<x<2, the bismuth oxide and bismuth niobate composite material is of a two-dimensional ultrathin nano sheet structure.
The bismuth oxide and bismuth niobate composite material is applied to removing algae in water.
In the technical scheme, the bismuth oxide and bismuth niobate composite material is used as a photocatalyst.
In the technical scheme, the bismuth oxide and bismuth niobate composite material is put into a water body containing algae under the illumination condition, and stirred.
The bismuth oxide and bismuth niobate composite material prepared by the invention can be used for removing harmful algae in water, has better oxygen activation capability and visible light response capability, and in addition, the photo-generated carrier recombination rate of the bismuth oxide and bismuth niobate composite material accelerates interlayer interface charge separation and transfer, so that the bismuth oxide and bismuth niobate composite material has higher photocatalytic activity.
Compared with the prior art, the invention has the following advantages:
1. the bismuth oxide and bismuth niobate composite material prepared by the invention has the characteristics of high photocatalytic activity, environmental protection, good stability and the like.
2. The bismuth oxide and bismuth niobate composite material is used for controlling cyanobacteria bloom in water, and is used for controlling O in air 2 The specific adsorption is better, so that electrons can flow from the catalyst to O 2 The electron transfer efficiency of the catalyst is higher, so that the effective electron quantity participating in oxygen activation is increased, and the photocatalytic algae removal effect is improved.
3. The bismuth oxide and bismuth niobate composite material (photocatalytic VDW heterojunction nano composite material) prepared by the invention accelerates interlayer interface charge separation and transfer through the formed VDW heterojunction, shortens charge transmission distance, thereby improving the separation rate of photoinduced electron hole pairs and obviously enhancing the photocatalytic activity of the catalyst.
Drawings
FIG. 1 shows Bi in examples 1 to 7 3 NbO 7 /BiO 2-x The efficiency of degrading chlorophyll a by photocatalysis by using the monomer/bismuth oxide and bismuth niobate composite material as a photocatalyst;
FIG. 2 is Bi 3 NbO 7 、BiO 2-x Monomer and Bi 3 NbO 7 /BiO 2-x The method comprises the steps of (1) changing Total Organic Carbon (TOC) of Extracellular (EOM) and Intracellular (IOM) organic matters in the photocatalytic algae killing process of a composite material, wherein a is extracellular, and b is intracellular;
FIG. 3 shows the stability of the photocatalytic killing experiment of the bismuth oxide and bismuth niobate composite material Microcystis aeruginosa prepared in example 4;
FIG. 4 is Bi 3 NbO 7 、BiO 2-x Monomer and Bi 3 NbO 7 /BiO 2-x X-ray diffraction pattern of the composite material;
FIG. 5 is a transmission electron micrograph of the bismuth oxide and bismuth niobate composite material prepared in example 4, wherein a is a TEM spectrum, b is a HRTEM spectrum, c is a HAADF-STEM spectrum, and d-g is an EDS element mapping spectrum;
FIG. 6 is Bi 3 NbO 7 、BiO 2-x Ultraviolet-visible diffuse reflection spectrum of the monomer and bismuth oxide and bismuth niobate composite material;
FIG. 7 is Bi 3 NbO 7 、BiO 2-x A surface photovoltaic test comparison graph of the monomer and bismuth oxide and bismuth niobate composite material;
FIG. 8 is Bi 3 NbO 7 、BiO 2-x And an EIS spectrogram and an instantaneous photocurrent response spectrogram of the monomer and bismuth oxide-bismuth niobate composite material, wherein a is the EIS spectrogram, and b is the instantaneous photocurrent response spectrogram.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The purity and manufacturer of the drug product according to the following examples are as follows:
| medicine name | Pharmaceutical molecular formula | Purity of | Reagent Co Ltd |
| Bismuth nitrate | Bi(NO 3 ) 3 ·6H 2 O | Analytical grade | Jiu Ding chemical (Shanghai) technology Co., ltd |
| Niobium oxalate | C 10 H 5 NbO 20 | Analytical grade | ShanghaiMicrophone Lin Biochemical technology Co.Ltd |
| Glacial acetic acid | CH 3 COOH | Analytical grade | Tianjin chemical reagent Co., ltd |
| Methanol | CH 3 OH | Analytical grade | TIANJIN FENGCHUAN CHEMICAL REAGENT Co.,Ltd. |
| Benzyl alcohol | C 6 H 5 CH 2 OH | Analytical grade | Tianjin chemical reagent Co., ltd |
| Potassium hydroxide | KOH | Analytical grade | TIANJIN KERMEL CHEMICAL REAGENT Co.,Ltd. |
| Sodium hydroxide | NaOH | Analytical grade | FUCHEN (TIANJIN) CHEMICAL REAGENT Co.,Ltd. |
| Absolute ethyl alcohol | CH 3 CH 2 OH | Analytical grade | Tianjin Fengshou chemical reagent technology Co.Ltd |
| Bismuth sodium acid | NaBiO 3 | Analytical grade | Roen chemical Co Ltd |
The types and manufacturers of the instruments involved in the following examples are as follows:
| model/specification | Instrument/device | Manufacturer (S) |
| CJB-S140 | Magnetic stirrer | TIANJIN KENUO INSTRUMENTS AND EQUIPMENT Co.,Ltd. |
| PHS-2F | Lei Ci pH meter | Shanghai Precision Scientific Instrument Co., Ltd. |
| 101-3A | Electrothermal constant temperature drying oven | Shanghai Saint Corp instruments Co., ltd |
| TG16-WS | Desk type high-speed centrifugal machine | Hunan Instrument centrifuge Co |
| CEL-HXF300-T3 | Xenon lamp light source | BEIJING CHINA EDUCATION AU-LIGHT Co.,Ltd. |
| 150ml | Double-layer beaker | Zhengzhou Xinyuan glass instrument |
| TOC-L CPN | Total organic carbon analyzer (TOC) | Shimadzu corporation of Japan |
| Max2200PC | X-ray diffractometer | Japanese Physics Co Ltd |
| JEM-2100F | Transmission electron microscope | Nippon Electronics Co., Ltd. |
| U-3900H | Ultraviolet-visible spectrophotometer | Japanese Hitachi Co Ltd |
| IPCE1000 | Surface photovoltage spectrometer | BEIJING PERFECTLIGHT SCIENCE AND TECHNOLOGY Ltd. |
| CHI760E | Electrochemical workstation | Shanghai Chenhua instruments Inc |
Example 1
Preparation of Bi 3 NbO 7 The method of (1) is as follows: slowly dripping the first solution into the second solution, stirring for 30min at room temperature of 20-25 ℃, adding benzyl alcohol, slowly adding 2mol/L potassium hydroxide aqueous solution to adjust the pH value to 13, transferring into a 100ml stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, preserving heat for 24h at 180 ℃, naturally cooling to room temperature, centrifuging, washing the solid obtained by centrifugation for 3 times by adopting deionized water and absolute ethyl alcohol, and drying for 8h at 80 ℃ in a drying box to obtain Bi 3 NbO 7 The preparation method of the first solution comprises the steps of mixing bismuth nitrate and glacial acetic acid, and stirring for 30min at the room temperature of 20-25 ℃; the preparation method of the second solution comprises the steps of mixing niobium oxalate and methanol, and stirring for 30min at the room temperature of 20-25 ℃; the ratio of the parts by weight of bismuth nitrate to the parts by volume of glacial acetic acid is 1.455:10, the ratio of the parts by weight of niobium oxalate to the parts by volume of methanol is 0.538:40, the unit of the parts by weight is g, the unit of the parts by volume is mL, and the ratio of the first solution to the second solution to the benzyl alcohol is 1:4:3.
example 2 (comparative)
BiO 2-x The preparation method of the monomer comprises the following steps:
mixing sodium hydroxide, sodium bismuthate and water, stirring at room temperature for 30min to uniformity, transferring to a 100ml stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, preserving heat at 180deg.C for 6h, naturally cooling to room temperature, centrifuging, washing the solid obtained by centrifuging with deionized water and absolute ethanol for 3 times, drying at 80deg.C in a drying oven for 8h, and grinding to obtain BiO 2-x The monomer, wherein the ratio of the mass parts of sodium hydroxide, the mass parts of sodium bismuthate and the volume parts of water is 2.4:2.8:60 parts by mass are in g and parts by volume are in mL.
Examples 3 to 7
Bismuth oxide and bismuth niobate composite material (Bi) for removing algae in water body 3 NbO 7 /BiO 2-x Composite material) preparation methodA method comprising the steps of:
mixing sodium hydroxide, sodium bismuthate and water, stirring at room temperature for 30min to uniformity, and adding Bi obtained in example 1 3 NbO 7 Stirring for 20min to uniformity at room temperature, transferring to a 100ml stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, preserving heat for 6h at 180 ℃, naturally cooling to room temperature, centrifuging, washing the solid obtained by centrifuging by adopting deionized water and absolute ethyl alcohol for 3 times, drying for 8h at 80 ℃ in a drying box, and grinding to obtain the bismuth oxide-bismuth niobate composite material, wherein the ratio of the mass parts of sodium hydroxide, the mass parts of sodium bismuthate and the volume parts of water is 2.4:2.8:60 parts by mass are in g and parts by volume are in mL. Bi in parts by mass 3 NbO 7 And sodium bismuthate is X, and X is shown in table 1.
TABLE 1
| Examples | X |
| Example 3 | 1:25 |
| Example 4 | 3:50 |
| Example 5 | 2:25 |
| Example 6 | 1:10 |
| Example 7 | 3:25 |
The microcystis aeruginosa photocatalytic kill experiments were performed in a 150ml double-layer beaker at room temperature of 20 ℃. The method for the photocatalysis killing experiment of the microcystis aeruginosa comprises the following steps: the double-layer beaker of 150ml contains microcystis aeruginosa liquid, the volume of the microcystis aeruginosa liquid is 150ml, and the concentration is 2.6X10 6 cells/ml. The illumination adopts a xenon lamp light source which provides visible light irradiation (wavelength>420 nm) with a light intensity of 100mW cm -1 . Chlorophyll a was used as an index for exploring the algicidal effect. 30mg of Bi from examples 1, 2, 3, 4, 5, 6 or 7 were taken 3 NbO 7 /BiO 2-x The monomer/bismuth oxide and bismuth niobate composite material is taken as a photocatalyst to be added into 150ml of microcystis aeruginosa liquid, and condensed water with the temperature of 15-20 ℃ is introduced into a double-layer beaker to ensure that the temperature of the microcystis aeruginosa liquid is kept at the room temperature of 20-30 ℃ in the reaction process. Continuously stirring during the photocatalytic reaction to ensure uniformity of contact between photocatalyst and algae cells, sampling every 30min to determine chlorophyll a content, and determining chlorophyll a content before degradation as C 0 . The experimental results are shown in FIG. 1.
Examples 1 to 7 show the efficiency of photocatalytic degradation of chlorophyll a as shown in FIG. 1, when Bi 3 NbO 7 The degradation efficiency of the photocatalytic reaction on chlorophyll a gradually increases when the mass ratio to sodium bismuthate increases from 1:25 to 3:50, whereas the degradation efficiency of the photocatalytic reaction on chlorophyll a decreases when the mass ratio increases again to 3:25. The photocatalytic algicidal efficiency of the bismuth oxide and bismuth niobate composite material prepared in example 4 is highest, and the degradation efficiency of the bismuth oxide and bismuth niobate composite material on chlorophyll a reaches 92% in 150 min.
Comparative examples 1, 2 and 4 changes in Total Organic Carbon (TOC) of Extracellular (EOM) and Intracellular (IOM) organics during photocatalytic algicidal process, and the results are shown in FIG. 2, in which TOC values and Bi of bismuth oxide and bismuth niobate composites 3 NbO 7 And BiO 2-x The monomer is significantly lower than the monomer, probably due to the more active species generated by the bismuth oxide and bismuth niobate composite under irradiation of visible light, thus promoting mineralization of EOM and IOM.
Investigation of Bi 3 NbO 7 /BiO 2-x Stability of the composite material. With the same Bi 3 NbO 7 /BiO 2-x The composite material was circulated as a photocatalyst for five times according to the above-mentioned method for the photocatalytic killing experiment of microcystis aeruginosa, and the results are shown in fig. 3 and table 2, wherein the photocatalyst was centrifuged with a table-type high-speed centrifuge after each method, and the centrifuged solid was washed 3 times with ethanol, dried at 80 ℃ for 3 hours, and subjected to the next circulation experiment, wherein the ethanol washing was centrifuging after ultrasonic treatment in ethanol for 10 minutes.
Table 2 shows the efficiency of chlorophyll a degradation per method and Bi at different times 3 NbO 7 /BiO 2-x The efficiency of degrading chlorophyll a of the composite material after five times of cyclic use can still reach 84%, which shows that Bi 3 NbO 7 /BiO 2-x The composite material has good stability and feasibility.
TABLE 2
FIG. 4 shows Bi obtained in examples 1, 2 and 4 3 NbO 7 、BiO 2-x X-ray diffraction pattern of the monomer and bismuth oxide and bismuth niobate composite material. As can be seen from FIG. 4, bi 3 NbO 7 And BiO 2-x The main diffraction peak of the monomer can be well matched with Bi 3 NbO 7 (JCPLDS 86-0875) and BiO 2-x (JCPDS 47-1057) one-to-one correspondence, no obvious Bi is found in the bismuth oxide and bismuth niobate composite material 3 NbO 7 Is mainly due to Bi 3 NbO 7 Is too low.
The bismuth oxide and bismuth niobate composite material prepared in example 4 was tested by using a JEM-2100F type Transmission Electron Microscope (TEM) to characterize the morphology and crystal structure. The results are shown in FIG. 5, in which the two-dimensional ultrathin nanosheet structure is shown in FIG. 5a, and Bi 3 NbO 7 Attached to BiO 2-x A surface. FIG. 5b is a high resolution TEM image of a bismuth oxide and bismuth niobate composite, showingObvious lattice fringes and Bi 3 NbO 7 The lattice spacing on the (200) plane is 0.27nm, biO 2-x The lattice spacing on the (111) plane is 0.318nm, which proves that the existence of two substances in the bismuth oxide and bismuth niobate composite material and the formation of heterojunction are favorable for the electron transmission between two phases, and can effectively inhibit the recombination of photo-generated electron-hole pairs, thereby obtaining high-efficiency photocatalytic activity. FIGS. 5c-g are elemental mapping maps showing the uniform distribution of Bi, O and Nb in the bismuth oxide and bismuth niobate composite, again confirming that the bismuth oxide and bismuth niobate composite is composed of Bi 3 NbO 7 And BiO 2-x Composition is prepared.
FIG. 6 shows Bi produced in examples 1, 2 and 4 3 NbO 7 、BiO 2-x Ultraviolet-visible absorption spectra of the monomer and bismuth oxide and bismuth niobate composites. As can be seen from the figure, when Bi 3 NbO 7 With BiO 2-x After the heterojunction is formed, the visible light absorption edge of the heterojunction shows a certain red shift phenomenon. Therefore, the light absorption capacity of the bismuth oxide-bismuth niobate composite material is higher than that of Bi 3 NbO 7 And BiO 2-x The monomer is greatly improved, and the bismuth oxide and bismuth niobate composite material can capture more visible light.
FIG. 7 shows Bi obtained in examples 1, 2 and 4 3 NbO 7 、BiO 2-x Steady state photovoltaic test patterns of the monomer and bismuth oxide and bismuth niobate composites were tested to provide monochromatic light by a 500W xenon lamp. It can be seen that the monomer BiO 2-x Shows a pronounced surface photovoltaic response in the 300-550nm range, however Bi 3 NbO 7 But hardly responded, indicating Bi 3 NbO 7 No photo-generated electron-hole separation occurs within its band gap. For the bismuth oxide and bismuth niobate composite material, the obvious enhancement of the photovoltaic signal is seen, and the photovoltaic curve of the bismuth oxide and bismuth niobate composite material is not simple Bi 3 NbO 7 And BiO 2-x Superposition of monomer signals. Thus, the formation of bismuth oxide and bismuth niobate composites is beneficial for the separation and transfer of photogenerated charges.
Bi prepared in examples 1, 2 and 4 3 NbO 7 、BiO 2-x The photoelectrochemical properties of the monomer and bismuth oxide and bismuth niobate composite material are studied: the electrochemical workstation of CHI760E and the three-electrode photochemical electrolytic cell are utilized, a platinum sheet is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and Bi is loaded 3 NbO 7 /BiO 2-x FTO conductive glass of monomer/bismuth oxide and bismuth niobate composite material is used as working electrode, and electrolyte is 0.5 mol.L -1 Na 2 SO 4 Electrochemical Impedance Spectroscopy (EIS) and transient photocurrent response tests were performed for the different catalysts. FIG. 8a is Bi 3 NbO 7 、BiO 2-x EIS spectrum of monomer and bismuth oxide and bismuth niobate composite material, and Bi 3 NbO 7 And BiO 2-x The half radius of bismuth oxide corresponding to bismuth niobate composite material is minimum compared with monomer, which shows that the interfacial charge transfer resistance is minimum, because of Bi 3 NbO 7 And BiO 2-x After recombination, charge transfer is promoted and recombination of electron-hole pairs is suppressed. FIG. 8b is Bi 3 NbO 7 、BiO 2-x Instantaneous photocurrent response spectrum of monomer and bismuth oxide-bismuth niobate composite material, and Bi 3 NbO 7 And BiO 2-x The bismuth oxide and bismuth niobate composite material shows stronger photocurrent response compared with the monomer, which proves that Bi 3 NbO 7 And BiO 2-x The heterojunction between the two is favorable for effectively separating electron-hole pairs, so that more photo-generated carriers perform photocatalysis reaction, and the photocatalysis activity is greatly improved.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (9)
1. The preparation method of the bismuth oxide and bismuth niobate composite material for removing algae in the water body is characterized by comprising the following steps: mixing sodium hydroxide, sodium bismuthate and water, adding Bi 3 NbO 7 Stirring uniformly at 170-180 DEG CPreserving heat for 5-8 h, centrifuging, washing and centrifuging to obtain a solid, and drying to obtain the bismuth oxide-bismuth niobate composite material, wherein the ratio of the mass parts of sodium hydroxide, the mass parts of sodium bismuthate and the volume parts of water is (2.3-2.4): (2.7-2.8): (50-60) the Bi comprises the following components in parts by weight 3 NbO 7 And sodium bismuthate (4-8): 100 parts by mass are expressed in g and parts by volume are expressed in mL.
2. The production method according to claim 1, wherein the Bi is produced 3 NbO 7 The method of (1) is as follows: dripping the first solution into the second solution, stirring at room temperature, adding benzyl alcohol, adjusting the pH to 10-15, preserving heat for 18-24 h at 170-180 ℃, centrifuging, washing the solid obtained by centrifugation, and drying to obtain the Bi 3 NbO 7 The first solution is a mixture of bismuth nitrate and glacial acetic acid, the second solution is a mixture of niobium oxalate and methanol, the ratio of the mass part of bismuth nitrate to the volume part of glacial acetic acid is (1.4-3): (10-20), the ratio of the mass part of niobium oxalate to the volume part of methanol is (0.5-1.1): (40-80), the unit of the mass part is g, the unit of the volume part is mL, and the ratio of the first solution, the second solution and benzyl alcohol is (1-2) according to the volume part: (4-8): (3-6).
3. The method according to claim 1 or 2, wherein the drying temperature is 70-80 ℃ and the drying time is 8-10 hours.
4. The method of claim 1 or 2, wherein the washing is performed with deionized water and absolute ethanol.
5. The bismuth oxide and bismuth niobate composite material obtained by the preparation method according to any one of claims 1 to 4.
6. Bismuth oxide according to claim 5 andthe bismuth niobate composite material is characterized in that the bismuth oxide and bismuth niobate composite material comprises: biO (BiO) 2-x Monomers and adhesion to BiO 2-x Bi on monomer surface 3 NbO 7 Particles, 0<x<2, the bismuth oxide and bismuth niobate composite material is of a two-dimensional ultrathin nano sheet structure.
7. The use of the bismuth oxide and bismuth niobate composite material according to claim 5 for removing algae in a body of water.
8. The use according to claim 7, characterized in that the bismuth oxide and bismuth niobate composite material acts as a photocatalyst.
9. The use according to claim 7, wherein the bismuth oxide and bismuth niobate composite material is put into a water body containing algae under illumination conditions and stirred.
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| US6664115B2 (en) * | 1992-10-23 | 2003-12-16 | Symetrix Corporation | Metal insulator structure with polarization-compatible buffer layer |
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| US4026950A (en) * | 1975-03-28 | 1977-05-31 | Rhone-Poulenc Industries | Process for the preparation of hydroxybenzaldehydes |
| CN101362084A (en) * | 2008-09-18 | 2009-02-11 | 武汉理工大学 | Visible-light response nano Bi3NbO7 photocatalyst preparation method and use thereof |
| CN108479751A (en) * | 2018-03-30 | 2018-09-04 | 王楷 | A kind of Bi-Bi3NbO7The preparation method and Bi-Bi of composite photo-catalyst3NbO7Composite photo-catalyst |
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