AU2020103306A4 - Preparation and application of a floating photocatalyst for inhibiting cyanobacteria in water - Google Patents
Preparation and application of a floating photocatalyst for inhibiting cyanobacteria in water Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000007667 floating Methods 0.000 title claims abstract description 34
- 241000192700 Cyanobacteria Species 0.000 title claims abstract description 25
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 13
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000010451 perlite Substances 0.000 claims abstract description 29
- 235000019362 perlite Nutrition 0.000 claims abstract description 24
- 239000002057 nanoflower Substances 0.000 claims abstract description 20
- 239000002070 nanowire Substances 0.000 claims abstract description 19
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 34
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 34
- 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 28
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 14
- 238000004729 solvothermal method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 238000003756 stirring Methods 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000005286 illumination Methods 0.000 abstract description 3
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 229910016267 Bi2 S3 Inorganic materials 0.000 abstract 2
- 239000000203 mixture Substances 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 241000195493 Cryptophyta Species 0.000 description 6
- 229930002868 chlorophyll a Natural products 0.000 description 6
- 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 6
- 238000000967 suction filtration Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000012851 eutrophication Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 241000192710 Microcystis aeruginosa Species 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003053 toxin Substances 0.000 description 3
- 231100000765 toxin Toxicity 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004904 UV filter Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000005422 algal bloom Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
- B01J2523/54—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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
- B01J2523/62—Sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2307/00—Location of water treatment or water treatment device
- C02F2307/14—Treatment of water in water supply networks, e.g. to prevent bacterial growth
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention, which belongs to the field of photocatalysts, presents a floating
photocatalyst for inhibiting cyanobacteria in water. The photocatalyst comprises expanded
perlite (EP), bismuth oxybromide (BiOBr) nano-flowers wrapped on the outer surface of the
EP and bismuth sulfide (Bi2 S3) nano-wires wound on the surface of the bismuth oxybromide
nano-flowers. In the invention, BiOBr displays higher chemical stability and excellent visible
light photocatalytic activity while Bi2 S3 has a larger sunlight absorption coefficient and an
excellent photoelectric conversion efficiency. The heterojunction formed at the interface of
Bi 2 S3 and BiOBr can improve the photocatalytic performance of the prepared photocatalyst.
Due to the excellent floating capability of EP, the obtained floating photocatalyst can
automatically float on water surface without stirring or under natural illumination. The
utilization of light and 02 in the photocatalytic reaction are improved to the maximum extent,
and greater photocatalytic efficiency is obtained. Besides, the floating catalyst is convenient
for large-area sprinkling and easy for intercepting and recovering, thus valuable for practical
developing.
Description
Preparation and application of a floating photocatalyst for inhibiting
cyanobacteria in water
[01] The invention relates to the field of photocatalyst technology, in particular to the preparation method and application of a floating photocatalyst for inhibiting cyanobacteria in water.
[02] The problem of eutrophication of water has become one of the most important environmental problems in China and around the world. With the increasing degree of the eutrophication of global water, the frequency of blooms of the poisonous and harmful algae, especially the cyanobacteria, is increasing, and the environmental and economic problems caused by eutrophication are attracting more and more attention. Meanwhile, with the improvement of the quality requirement of drinking water, the algal toxin pollution caused by cyanobacteria blooms is becoming of increasing concern. Therefore, it is imperative to reduce the eutrophication degree of water body and to seek effective ways to prevent and control harmful algal blooms and algal toxin pollution.
[03] Photocatalytic technology, which can convert the light energy to chemical energy by using the semiconductor material as photocatalyst, is popular because of the advantages in environmental protection and the technological simplicity. Many researchers have applied photocatalytic technology to control algal blooms and harmful red tides, and made some progress. By using the photocatalysis technology, the algal toxin released by the dead algae can be gradually degraded into nontoxic acids and aldehyde oxides during inactivating the algae, without causing secondary pollution; and the whole treatment reaction process is simple. In addition, from the point of view of energy conservation, algae, which need photosynthesis to grow and reproduce, usually grow in the place with enough light source. This characteristic is just beneficial to the practical implementation of the photocatalytic algae removal technology. However, the conventional nano-powder photocatalysts have some defects in treating a large range of algae in water. For example, the nano-powder photocatalyst is easy to agglomerate to settle in water, leading to insufficient utilization of light, thus low efficiency. Besides, the catalyst is difficult to recover and reuse, and even causes secondary pollution.
[04] Therefore, the present invention aims to provide the preparation method and application of a floating photocatalyst for inhibiting cyanobacteria in water, and the advantages of the photocatalyst presented in this invention include higher cyanobacteria removal efficiency, easy recovery and no secondary pollution.
[05] In order to achieve the above objectives, the present invention provides the following technical scheme:
[06] A floating photocatalyst for inhibiting cyanobacteria in water comprises the expanded-perlite, bismuth oxybromide nano-flowers wrapped on the outer surface of the expanded-perlite and bismuth sulfide nano-wires wound on the surface of the bismuth oxybromide nano-flowers.
[07] Preferably, the ratio of the mass of expanded perlite to the amount of substance of bismuth oxybromide nano-flowers and to the amount of substance of bismuth sulfide nano-wires is 0.5-1 g:1-3 mol:0.7 mol.
[08] Preferably, the diameter of the bismuth oxybromide nano-flower is 2-3 [m.
[09] Preferably, the diameter of the bismuth sulfide nano-wire is 20-50 nm, and the length of the bismuth sulfide nano-wire is 100-300 nm.
[010] Preferably, the particle size of the expanded perlite is 200-250 m, and the flotation rate of the expanded perlite is 90-98%.
[011] The invention also presents the preparation method of the photocatalyst in the above technical scheme, which comprises the following steps:
[012] Mixing bismuth nitrate and ethylene glycol monomethylether to obtain a bismuth nitrate solution;
[013] Mixing thiourea, potassium bromide, ethylene glycol monomethylether and expanded perlite to obtain a mixed feed liquor;
[014] Dripping the bismuth nitrate solution into the mixed feed liquor to obtain a suspension;
[015] And carrying out solvothermal reaction with the suspension to obtain the floating photocatalyst for inhibiting cyanobacteria in water.
[016] Preferably, the molar ratio of bismuth nitrate to thiourea and to potassium bromide is 1:1-3:0.7.
[017] Preferably, the concentration of the bismuth nitrate solution is 0.1-0.3 mol/L, and the dropping rate is 2-4 mL/min.
[018] Preferably, the temperature of the solvothermal reaction is 120-150 °C, and the time of the solvothermal reaction is 12-24 h.
[019] The invention also presents the application in inhibiting cyanobacteria of the photocatalyst in the technical scheme or prepared by the preparation method in the technical scheme.
[020] The invention presents a floating photocatalyst (EP-Bi 2S 3/BiOBr) for inhibiting cyanobacteria in water, which comprises the expanded-perlite (EP), bismuth oxybromide (BiOBr) nano-flowers wrapped on the outer surface of the EP and bismuth sulfide (Bi 2 S 3 ) nano-wires wound on the surface of the bismuth oxybromide nano flowers. In the invention, BiOBr displays higher chemical stability and excellent visible light photocatalytic activity, while Bi 2 S 3 has a larger sunlight absorption coefficient and an excellent photoelectric conversion efficiency. The heterojunction formed at the interface of Bi 2 S 3 and BiOBr can improve the photocatalytic performance of the prepared photocatalyst. Due to the excellent floating capability of EP, the obtained floating photocatalyst can automatically float on water surface without stirring or under natural illumination. The utilization of light and 02 in the photocatalytic reaction are improved to the maximum extent, and greater photocatalytic efficiency is obtained. Besides, the floating catalyst without any secondary pollution is convenient for large area sprinkling and easy for intercepting and recovering, thus valuable for practical developing. The data of the examples show that the floating photocatalyst for inhibiting the cyanobacteria in water in this invention has a removal rate of chlorophyll a of
70.21% under the irradiation of simulated sunlight with the wavelength X> 420nm, and the floating rate of 7 5 - 8 5 % is still maintained after one week.
[021] The present invention will now be further detailed with reference to the figures and specific implementation.
[022] Figure 1 is an XRD diffraction pattern of EP-Bi 2S 3, EP-BiOBr and the EP Bi2S3/BiOBr photocatalyst prepared in Example 1 according to the present invention;
[023] Figure 2 is an SEM diffraction pattern of EP-Bi 2S 3 , EP-BiOBr and the EP Bi2S3/BiOBr photocatalyst prepared in Example 1 according to the present invention;
[024] Figure 3 shows the curves of the removal efficiency of chlorophyll a by the cyanobacteria under visible light by EP-Bi 2S 3 , EP-BiOBr and the EP-Bi 2S 3/BiOBr photocatalyst prepared in Example 1 according to the present invention;
[025] Figure 4 is a test curve for the floating capability of EP-Bi 2 S 3 , EP-BiOBr according to the invention and the EP-Bi 2S 3/BiOBr photocatalyst prepared in Example 1.
[026] The invention presents a floating photocatalyst for inhibiting cyanobacteria in water, which comprises the expanded-perlite, bismuth oxybromide nano-flowers wrapped on the outer surface of the expanded-perlite and bismuth sulfide nano-wires wound on the surface of the bismuth oxybromide nano-flowers.
[027] In the present invention, the ratio of the mass of expanded perlite to the amount of substance of bismuth oxybromide nano-flowers and to the amount of substance of bismuth sulfide nano-wires is preferably 0.5-1 g:1-3 mol:0.7 mol, more preferably 1 g:2.4 mol:0.7 mol.
[028] In the present invention, the diameter of the bismuth oxybromide nano flower is preferably 2-3 m, more preferably 2.4-2.6 m.
[029] In the present invention, the diameter of the bismuth sulfide nano-wire is preferably 20-50 nm, more preferably 30-40 nm, and the length of the bismuth sulfide nano-wire is preferably 100-300 nm, more preferably 200-250 nm.
[030] In the present invention, the diameter of the expanded perlite particles is preferably 200-250 m, more preferably 220-230 m. In the present invention, the floating rate of the expanded perlite is preferably 90-98%, more preferably 95-98%. In this invention, the expanded perlite (EP) has an air bubble filled foam structure formed by rapidly losing moisture and expanding of the volcanic rocks at high temperature, and the main chemical composition is SiO 2 and A1 2 0 3 . Due to its good floating capability, the expanded perlite (EP) can be used to prepare the floating photocatalyst, which can automatically float on the water surface without stirring or under natural illumination. The utilization of light and 02 in the photocatalytic reaction is improved to the maximum extent, and greater photocatalytic efficiency is obtained. Besides, the floating catalyst without any secondary pollution is convenient for large-area sprinkling and easy for intercepting and recovering, thus valuable for practical developing. The present invention is not particularly limited to the source of the expanded perlite, and may be applied to commercial products well known to those skilled in the art.
[031] The invention also provides the preparation method of the photocatalyst in the above technical scheme, which comprises the following steps:
[032] Mixing bismuth nitrate and ethylene glycol monomethylether to obtain a bismuth nitrate solution;
[033] Mixing thiourea, potassium bromide, ethylene glycol monomethylether and expanded perlite to obtain a mixed feed liquor;
[034] Dripping the bismuth nitrate solution into the mixed feed liquor to obtain a suspension;
[035] And carrying out solvothermal reaction with the suspension to obtain the floating photocatalyst for inhibiting cyanobacteria in water.
[036] In this invention, the bismuth nitrate and ethylene glycol monomethylether are mixed to obtain a bismuth nitrate solution. In the present invention, the concentration of the bismuth nitrate solution is preferably 0.1-0.3 mol/L, more preferably 0.2-0.25 mol/L. In the invention, the ultrasonic mixing is preferable, and the time and the power of the ultrasonic are not particularly limited, as the bismuth nitrate and the ethylene glycol monomethylether can be uniformly mixed, specifically, the ultrasonic time is preferably 15 min.
[037] In this invention, the thiourea, potassium bromide, ethylene glycol monomethylether and expanded perlite are mixed to obtain a mixed feed liquor. In the present invention, the adding sequence of the thiourea, the potassium bromide, the ethylene glycol monomethylether and the expanded perlite is not particularly limited, and the adding sequence which is well known to those skilled in the art can be adopted. Specifically, after the thiourea and the potassium bromide are dissolved in the ethylene glycol monomethylether together, ultrasonic treatment is carried out, and the expanded perlite is added followed by mechanical stirring. In this invention, the ultrasonic time and power are not particularly limited, and the thiourea, the potassium bromide and the ethylene glycol monomethylether can be uniformly mixed. Specifically, the ultrasonic time is preferably 15 min. In the present invention, the rotation speed of the mechanical stirring is preferably 200-500 rpm, more preferably 300-400 rpm, and the time of the mechanical stirring is preferably 20-50 min, more preferably 30-40 min. In the present invention, the mechanical stirring can avoid the EP pulverization and cause the surface of the EP to be coated with thiourea and potassium bromide.
[038] In the present invention, the molar ratio of bismuth nitrate to thiourea and to potassium bromide is preferably 1:1-3:0.7, more preferably 1:2.4:0.7. In the present invention, the ratio of the mass of the expanded perlite to the amount of substance of the potassium bromide is preferably 0.5-1 g:0.7 mol. more preferably 1 g:0.7 mol.
[039] In the present invention, the volume ratio of the amount of the thiourea substance to the ethylene glycol monomethylether at the time of preparing the mixed liquor is preferably 2-3 mol:30 mL, more preferably 2.4 mol:30 mL.
[040] After the bismuth nitrate solution and the mixed feed liquor are respectively obtained, the bismuth nitrate solution is dripped into the mixed feed liquor to obtain a suspension. In the present invention, the rate of the dropwise addition is preferably 2-4 mL/min, more preferably 3-3.5 mL/min. In the invention, the dripping can ensure that the components are uniformly mixed, and the bismuth oxybromide nano-flowers and the bismuth sulfide nano-wires are generated on the surface of the expanded perlite in situ in the process of solvent thermal reaction, so that the bismuth oxybromide nano flowers and the bismuth sulfide nano-wires can be sequentially wrapped on the surface of the expanded perlite, and the bismuth sulfide nano-wires can be deposited on the surface of the bismuth oxybromide nano-flowers.
[041] Then, the obtained suspension is subjected to solvothermal reaction to obtain the floating photocatalyst for inhibiting cyanobacteria in water. In the present invention, the temperature for the solvothermal reaction is preferably 120-150 °C, more preferably 130-140 °C; and the reaction time is preferably 12-24 h, more preferably 18 22 h.
[042] In the present invention, the solvothermal reaction of the suspension is preferably conducted after standing. In the present invention, the standing time is preferably 20-50 min, more preferably 30-40 min.
[043] In the present invent, the device for the solvothermal reaction is not particularly limited, and the reaction device well known to those skilled in the art can be used, and specifically, such as the high-pressure reactor.
[044] After the solvothermal reaction, the invention preferably carries out solid liquid separation of the reaction product, washing and drying in sequence to obtain the floating photocatalyst for inhibiting cyanobacteria in water. In the present invention, the solid-liquid separation is preferably a suction filtration.
[045] In this invention, the solid product obtained by the suction filtration is washed. In the present invention, the water washing is the most preferred method, and the amount of the water used and the number of the water washing are not particularly limited in the present invention, and it can be carried out in a manner well known to those skilled in the art.
[046] After the water washing is finished, the water washing product is dried to obtain the floating photocatalyst for inhibiting the cyanobacteria in the water. In the present invention, the drying temperature and the drying time are not particularly limited, as the water in the aqueous product can be removed. Specifically, the drying is carried out at, for example, 60 °C for 6 h.
[047] The invention also presents the application in inhibiting cyanobacteria of the photocatalyst in the above technical scheme or prepared by the preparation method in the technical scheme.
[048] In the present invention, the ratio of the photocatalyst mass to the cyanobacteria concentration in the algal solution is preferably 0.05-0.25 g:2.8x108 cell-L-1, and more preferably 0.2 g:2.8x108 cell-L-'.
[049] Next, the floating photocatalyst for inhibiting cyanobacteria in water and its preparation method and application in the present invention are detailed with reference to examples, but they are not to be construed as limiting the scope of protection of the present invention.
[050] Example 1
[051] Adding 1 mmol of Bi(N0 3 ) 3 -5H2 0 into 10 mL of ethylene glycol monomethylether, followed by a 15 minute-ultrasonic treatment to obtain a colorless bismuth nitrate solution; Dissolving 2.4 mmol of thiourea and 0.7 mmol of KBr into 30 mL of ethylene glycol monomethylether, followed by a 15 minute-ultrasonic treatment, and stirring until a colorless transparent solution is obtained; Weighing 1 g of EP, adding into the colorless transparent solution, and mechanically stirring for 30 minutes to obtain a mixture; Dropwise adding the bismuth nitrate solution into the mixture under mechanical stirring, to obtain a uniform yellow EP suspension, and standing for 30 minutes, then transferring to a high-pressure reactor and reacting for 12 hours at a temperature of 120 °C. After natural cooling, the product is separated from the sample by the suction filtration, washed with a large amount of deionized water, and dried at the temperature of 60 °C to obtain the brown EP- Bi2S3/BiOBr.
[052] Example 2
[053] Adding 1.5 mmol of Bi(N0 3 ) 3 -5H2 0 into 10 mL of ethylene glycol monomethylether, followed by a 15 minute-ultrasonic treatment to obtain a colorless bismuth nitrate solution; Dissolving 2.4 mmol of thiourea and 0.7 mmol of KBr into 30 mL of ethylene glycol monomethylether, followed by a 15 minute-ultrasonic treatment, and stirring until a colorless transparent solution is obtained; Weighing 1 g of EP, adding into the colorless transparent solution, and mechanically stirring for 30 minutes to obtain a mixture; Dropwise adding the bismuth nitrate solution into the mixture under mechanical stirring, to obtain a uniform yellow EP suspension, and standing for 30 minutes, then transferring to a high-pressure reactor and reacting for 18 hours at a temperature of 130 °C. After natural cooling, the product is separated from the sample by the suction filtration, washed with a large amount of deionized water, and dried at the temperature of 60 °C to obtain the brown EP- Bi2S3/BiOBr.
[054] Example 3
[055] Adding 2 mmol of Bi(N03)3-5H20 into 10 mL of ethylene glycol monomethylether, followed by a 15 minute-ultrasonic treatment to obtain a colorless bismuth nitrate solution; Dissolving 2.4 mmol of thiourea and 0.7 mmol of KBr into 30 mL of ethylene glycol monomethylether, followed by a 15 minute-ultrasonic treatment, and stirring until a colorless transparent solution is obtained; Weighing 1 g of EP, adding into the colorless transparent solution, and mechanically stirring for 30 minutes to obtain a mixture; Dropwise adding the bismuth nitrate solution into the mixture under mechanical stirring, to obtain a uniform yellow EP suspension, and standing for 30 minutes, then transferring to a high-pressure reactor, reacting for 22 hours at a temperature of 140 °C. After natural cooling, the product is separated from the sample by the suction filtration, washed with a large amount of deionized water, and dried at the temperature of 60 °C to obtain the brown EP- Bi2S3/BiOBr.
[056] Example 4
[057] Adding 3 mmol of Bi(N03)3-5H20 into 10 mL of ethylene glycol monomethylether, followed by a 15 minute-ultrasonic treatment to obtain a colorless bismuth nitrate solution; Dissolving 2.4 mmol of thiourea and 0.7 mmol of KBr into 30 mL of ethylene glycol monomethylether, followed by a 15 minute-ultrasonic treatment, and stirring until a colorless transparent solution is obtained; Weighing 1 g of EP, adding into the colorless transparent solution, and mechanically stirring for 30 minutes to obtain a mixture; Dropwise adding the bismuth nitrate solution into the mixture under mechanical stirring, to obtain a uniform yellow EP suspension, and standing for 30 minutes, then transferring to a high-pressure reactor and reacting for 24 hours at a temperature of 150 °C. After natural cooling, the product is separated from the sample by the suction filtration, washed with a large amount of deionized water, and dried at the temperature of 60 °C to obtain the brown EP- Bi2S3/BiOBr.
[058] Comparative Example 1
[059] The EP-Bi 2 S 3 catalyst is prepared by the method in Example 1 for preparing EP-Bi 2 S 3 without adding KBr, and the remaining steps are the same.
[060] Comparative Example 2
[061] The EP-BiOBr catalyst is prepared by the method in Example 1 for preparing EP-BiOBr without adding thiourea, and the remaining steps are the same.
[062] The XRD diffraction patterns of the EP-Bi 2 S 3 , EP-BiOBr and EP Bi2S3/BiOBr photocatalyst prepared in Example 1 are shown in Figure 1. From Figure 1, the characteristic peak of EP-Bi 2 S 3 coincides with the standard card of monoclinic Bi 2 S 3 (PDF#17-0320). The characteristic diffraction peak of EP-BiOBr is in good agreement with the standard card of tetragonal BiOBr (PDF#09-0393). The EP Bi2S3/BiOBr shows the main diffraction peak of these two components, indicating the crystal form has not changed. But the main diffraction peak is partially coincident with the diffraction peak of BiOBr because of the low content of Bi2 S 3 .
[063] The SEM patterns of the EP-Bi 2 S 3, EP-BiOBr and EP-Bi 2S 3/BiOBr photocatalyst prepared in Example 1are shown in Figure 2, where a is EP, b is EP Bi 2 S 3 , c is EP-BiOBr, and d is EP-Bi 2 S 3/BiOBr. From this figure, EP is a smooth porous material, the prepared pure EP-Bi 2 S 3 has a nano-flower-like structure consisting of nano-wires, the pure EP-BiOBr has a nano-flower-like structure consisting of nano sheets, and the composite material of EP-Bi 2S 3/BiOBr shows a feature of nano-flowers covered with and wounded by nano-wires, which indicates that Bi2 S 3 and BiOBr are fully filled. The p-n heterojunction is formed at the boundary of these two components, which hinders the recombination of electrons and holes, and improves the light absorption performance and the catalytic activity of the catalyst.
[064] The EP-Bi 2 S 3, EP-BiOBr and EP-Bi 2S 3/BiOBr photocatalyst prepared in Example 1 can remove the chlorophyll a from cyanobacteria microcystis aeruginosa under the radiation of visible light, and the comparative results are shown in Figure 3. Adding 0.2 g of the EP-Bi 2S 3/BiOBr photocatalyst prepared in Example 1 into 200 mL of microcystis aeruginosa (2.8x108 cell-L-1), and the removal rate of chlorophyll a is 70.21% after a 5 h-irradiation of simulated sunlight (Xenon lamp, 300 W, with UV filter) with a wavelength X>420 nm. In the comparative experiment, the content of chlorophyll a increases within 5 hours when the single EP-Bi 2 S 3 is used as the photocatalyst to degrade the microcystis aeruginosa, while the removal rate of chlorophyll a in 5 hours is 25.26% when the single EP-BiOBr is used. It can be seen that the results with EP-Bi 2 S 3/BiOBr photocatalyst is superior to the comparative ones.
[065] The floating performance tests of the EP-Bi 2 S 3, EP-BiOBr and EP Bi2S3/BiOBr photocatalyst prepared in Example 1 are shown in Figure 4. From Figure 4, the EP-Bi 2 S 3/BiOBr photocatalyst prepared in Example 1 still retains a floating rate of 75-85% over a period of one week. The practical algal bloom water area has a large treatment period and needs to be subjected to photocatalytic treatment for a long time. The floating photocatalyst should meet the floating effect for a certain duration. The suspension in water can increase the utilization rate of the light energy and the amount of the photo-generated electron-hole pairs, leading to an improved photocatalysis efficiency.
[066] Although the invention has been described with reference to specific examples, it will be appreciated by those skilled in the art that the invention may be embodied in many other forms, in keeping with the broad principles and the spirit of the invention described herein.
[067] The present invention and the described embodiments specifically include the best method known to the applicant of performing the invention. The present invention and the described preferred embodiments specifically include at least one feature that is industrially applicable
Claims (10)
1. A type of floating photocatalyst for inhibiting cyanobacteria in water comprising the expanded perlite, bismuth oxybromide nano-flowers wrapped on the outer surface of the expanded perlite, and bismuth sulfide nano-wires wrapped on the surface of the bismuth oxybromide nano-flowers.
2. The photocatalyst in Claim 1, wherein the ratio of the mass of the expanded perlite to the amount of substance of the bismuth oxybromide nano-flower and to the amount of substance of the bismuth sulfide nano-wire is 0.5-1 g:1-3 mol:0.7 mol.
3. The photocatalyst in Claims 1 and 2, wherein the diameter of the bismuth oxybromide nano-flower is 2-3 m.
4. The photocatalyst in Claim 3, wherein the diameter of the bismuth sulfide nano-wire is 20-50 nm, and the length of the bismuth sulfide nano-wire is 100-300 nm.
5. The photocatalyst in Claim 1, wherein the particle diameter of the expanded perlite is 200-250 m, and the floating rate of the expanded perlite is 95-98%.
6. The preparation method of the photocatalyst in Claims 1-5, comprising the following steps:
Mixing bismuth nitrate and ethylene glycol monomethylether to obtain a bismuth nitrate solution;
Mixing thiourea, potassium bromide, ethylene glycol monomethylether and expanded perlite to obtain a mixed feed liquor;
Dripping the bismuth nitrate solution into the mixed feed liquor to obtain a suspension;
And carrying out solvothermal reaction with the suspension to obtain the floating photocatalyst for inhibiting cyanobacteria in water.
7. The method according to Claim 6, wherein the molar ratio of bismuth nitrate to thiourea, and to potassium bromide is 1:1-3:0.7.
8. The preparation method in Claim 6, wherein the concentration of the bismuth nitrate solution is 0.1-0.3 mol/L, and the dropping rate is 2-4 mL/min.
9. The preparation method in Claim 6, wherein the temperature of the solvent thermal reaction is 120-150 °C, and the time of the solvent thermal reaction is 12-24 h.
10. The application of the photocatalyst according to any one of Claims 1-5 or the photocatalyst by the preparation method according to any one of Claims 6-9 for inhibiting cyanobacteria.
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