CN110270376A - Photocatalysis sponge and its preparation method and application for removing algae and water - Google Patents
Photocatalysis sponge and its preparation method and application for removing algae and water Download PDFInfo
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- CN110270376A CN110270376A CN201910653430.6A CN201910653430A CN110270376A CN 110270376 A CN110270376 A CN 110270376A CN 201910653430 A CN201910653430 A CN 201910653430A CN 110270376 A CN110270376 A CN 110270376A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 241000195493 Cryptophyta Species 0.000 title claims abstract description 78
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 70
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 63
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 63
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 49
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000004064 recycling Methods 0.000 abstract 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 15
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 6
- 241000192700 Cyanobacteria Species 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 229930002868 chlorophyll a Natural products 0.000 description 4
- 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 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 230000007306 turnover Effects 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 241000628997 Flos Species 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003053 toxin Substances 0.000 description 2
- 231100000765 toxin Toxicity 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 241001465754 Metazoa Species 0.000 description 1
- 241000192710 Microcystis aeruginosa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 108010067094 microcystin Proteins 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- -1 zeolite imidazole ester Chemical class 0.000 description 1
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
-
- B01J35/39—
-
- 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
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
-
- 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
Abstract
The present invention relates to a kind of preparation method for removing the photocatalysis sponge of algae and water and the photocatalysis sponges for removing algae and water and its application.The preparation method of the photocatalysis sponge for being used to remove algae and water includes the following steps: the aqueous solution soaking sponge using Ag/AgCl@ZIF-8, obtains the wet sample of photocatalysis sponge；The dry above-mentioned wet sample of photocatalysis sponge, obtains the photocatalysis sponge for removing algae and water.The photocatalysis sponge that above-mentioned preparation method obtains floats on water surface based on the buoyancy of sponge, can directly utilize photon energy, to improve photochemical catalyst to the utilization rate of photon；Buoyancy based on sponge floats on water surface, can directly contact in the algae that wawter bloom occurs, and removes algae efficiency to improve；And the crumb structure based on sponge, convenient for recycling.
Description
Technical field
The present invention relates to water-treatment technology fields, more particularly to a kind of for removing the photocatalysis sponge of algae and water
Preparation method and photocatalysis sponge for removing algae and water and its application.
Background technique
With the quickening of global warming and process of industrialization, water eutrophication caused by nitrogen and phosphorus element leads to indigo plant
The phenomenon that algae breakout of water bloom, is more serious.Cyanobacteria mass propagation can consume the dissolved oxygen in water, decline the light transmittance of water body, pH
It changes, the living environment of aquatic animals and plants is on the hazard.Toxicity extremely strong Microcystin can be discharged when cyanobacteria death, it is micro-
Capsule algae toxin is extremely stable in water, has difficult for biological degradation and persistence, it is difficult to be removed by traditional water treatment technology.Together
When cyanobacteria can hinder flocculation sedimentation process influence drinking water quality.In addition, the release of organic matter can make in water in Cells of Blue-green Algae
Total dissolved organic carbon content increases, and is easy to produce disinfection by-products in chlorination treatment process, increases water treatment procedure
Difficulty and cost.
Photocatalysis technology is one of current improvement common technology of cyanobacterial bloom, which can be carried out light using the sun
Algal grown is killed or inhibited to catalytic oxidation.Because of easy, at low cost, thorough to contaminant degradation and nothing two that the energy obtains
The advantages of secondary pollution and by favor.The active height of nano-photocatalyst material, chemical stability are good, nontoxic, particle is easy easily
, low in cost, abundant raw material, strong adsorption capacity the advantages that, be most popular one of photochemical catalyst, be widely used in all kinds of
Photocatalysis oxidation reaction.Nano-photocatalyst and microbial interaction can produce reactive oxygen species, and reactive oxygen species can not only kill
Microorganism killing (such as cyanobacteria, bacterium), moreover it is possible to which various chemical pollutants of degrading (such as degradation algae toxin, stink substances), are one
It plants effective, low-cost bloom blue algae and controls new method.
But there is also some problems: (1) photocatalysis for application of the currently used nano-photocatalyst in practical water body
Agent system is essentially suspension system, bad to the treatment effect for the algae for being grown on water surface；(2) photochemical catalyst is actually being answered
It is not easily recycled in, secondary pollution may be generated to environment.
Summary of the invention
Based on this, it is necessary to provide it is a kind of be capable of handling water surface algae and easily recycle for removing algae and water
The preparation method of photocatalysis sponge.
In addition, the photocatalysis sponge for removing algae and water for also providing that a kind of above method is prepared and its answer
With.
It is a kind of for removing the preparation method of the photocatalysis sponge of algae and water, include the following steps:
Using the aqueous solution soaking sponge of Ag/AgCl@ZIF-8, the wet sample of photocatalysis sponge is obtained；
The dry wet sample of photocatalysis sponge, obtains the photocatalysis sponge for removing algae and water.
Currently used photochemical catalyst system is essentially suspension system, the homogeneous pollutant being only applicable in water body, uncomfortable
Symphysis is longer than the algae of water surface, and existing photochemical catalyst is substantially powdered, is not easily recycled in the application, may
Secondary pollution is generated to environment.And it above-mentioned is used for using what sponge loaded composite photocatalysis agent Ag/AgCl@ZIF-8 was prepared
The photocatalysis sponge for removing algae and water, since the buoyancy of sponge can float on the water surface of generation wawter bloom, and Ag/
AgCl@ZIF-8 can directly utilize photon energy, so as to efficiently dispose the algae of water surface；And in utilization
The photocatalysis sponge for removing algae and water that the method for stating is prepared is crumb structure, is easy recovery processing.
In one of the embodiments, the photocatalysis sponge obtained for removing algae and water the wet sample the step of it
Before, include the steps that the sponge impregnate using surfactant solution modified.
It is described in one of the embodiments, that the sponge is carried out using surfactant to impregnate modified step packet
It includes:
The sponge is impregnated using surfactant solution；
The sponge is taken out, the surfactant solution extra on the sponge is disposed；
The dry sponge, obtains modified sponge.
The surfactant solution is neopelex solution in one of the embodiments,.
The Ag/AgCl@ZIF-8 needs to use AgNO in synthesis in one of the embodiments,3Solution and NaCl are molten
Liquid, the AgNO3The solvent of solution is deionized water and dehydrated alcohol, the volume ratio of the deionized water and the dehydrated alcohol
It is 1: 3~1: 6；The solvent of the NaCl solution is deionized water and dehydrated alcohol, the deionized water and the dehydrated alcohol
Volume ratio be 1: 3~1: 6.
In one of the embodiments, in the Ag/AgCl@ZIF-8 Ag/AgCl mass percentage be 20%~
50%.
The mass percentage of Ag/AgCl is 35% in the Ag/AgCl@ZIF-8 in one of the embodiments,.
It is a kind of for removing the photocatalysis sponge of algae and water, the photocatalysis sponge for removing algae and water includes
Modified sponge and the Ag/AgCl@ZIF-8 being adsorbed on the modified sponge.
The above-mentioned photocatalysis sponge for removing algae and water is in the application administered in wawter bloom.
The wawter bloom is cyanobacterial bloom in one of the embodiments,.
Detailed description of the invention
Fig. 1 is the sponge for the photocatalysis sponge and comparative example 1 for removing algae and water that Examples 1 to 5 is prepared
Handle the effect contrast figure of microcystic aeruginosa；
Fig. 2 is the structural schematic diagram of the Ag/AgCl@ZIF-8 of an embodiment；
Fig. 3 is the structural schematic diagram of the photocatalysis sponge for removing algae and water of an embodiment.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give preferred embodiment of the invention.But the invention can be realized in many different forms, however it is not limited to herein
Described embodiment.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more saturating
It is thorough comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body is not to be to limit the present invention.
Herein during photocatalysis sponge of the preparation for removing algae and water, the water being previously mentioned or so-and-so is molten
The aqueous solution of agent, " water " therein, which refers to, utilizes various water treatment technologies, as much as possible removing suspended matter, colloid and inorganic sun
After the impurities in water such as ion, anion, obtained deionized water can also be substituted if having ready conditions with high purity water.
The preparation method of the photocatalysis sponge for removing algae and water of one embodiment, includes the following steps:
Step S100: immersion modification is carried out to sponge using surfactant solution.It is appreciated that sponge has very much
Hole and great specific surface area, density of the density well below water body.Consider for cost and application effect, above-mentioned surface
Activating agent selects neopelex.
Wherein, the sponge in step S100 is preferably polyurethane sponge.It should be noted that sponge used herein is not
It is limited to polyurethane sponge, all energy loaded optic catalyst Ag/AgCl@ZIF-8 and the porous media material for swimming in water surface
Material is contemplated that.
Specifically, step S100 includes:
Step S110: above-mentioned sponge is impregnated using surfactant solution.Specifically, step S110 include: take 2 it is above-mentioned
Sponge is soaked in surfactant solution, oscillating contact 30min or more；Come into full contact with sponge with surfactant.It needs
Illustrate, be found through experiments that, during being modified to sponge, impregnates 2 simultaneously every time using surfactant solution
Modified effect when piece sponge is best.
Step S120: the sponge in step S100 is taken out, surfactant solution extra on sponge is disposed.Specifically
Ground, step S120 include: to be impregnated to wash away surfactant solution extra on the sponge in step S110 with deionized water.
Step S130: the sponge in drying steps S120 obtains modified sponge.The purpose of step S130 is to wave moisture
Hair.
Step S200: using the above-mentioned sponge of aqueous solution soaking of Ag/AgCl@ZIF-8, the wet sample of photocatalysis sponge is obtained.
Referring to Fig. 2, the Ag/AgCl@ZIF-8 in step S200 is the zeolite imidazole ester bone of a kind of loaded Ag and its villaumite
Frame structural material (ZIF-8).Ag/AgCl@ZIF-8 is a kind of NEW TYPE OF COMPOSITE photochemical catalyst that developed in recent years, its conjunction
At method in document (Gongduan Fan, Xiaomei Zheng, Jing Luo, et al., 2018.Rapid synthesis
of Ag/AgCl@ZIF-8as a highly efficient photocatalyst for degradation of
Acetaminophen under visible light.Chemical Engineering Journal, 351:782-790) in
There is play-by-play.It is only briefly described herein: ZIF-8 is dissolved in AgNO3(solvent is deionized water and anhydrous second to solution
Volume ratio 1: 3~1: alcohol in 6), stirs 3h at room temperature；It is molten that NaCl is added dropwise in above-mentioned mixed solution in 20min
(solvent is deionized water and dehydrated alcohol to liquid, volume ratio 1: 3~1: 6) in, obtains bluish violet product after stirring 10h；Centrifugation
After be washed with deionized three times to remove excess NaCl, obtain Ag/AgCl@ZIF-8 after dry 12h at 70 DEG C.
The configuration method of the aqueous solution of Ag/AgCl@ZIF-8 in step S200 are as follows: Ag/AgCl@ZIF-8 is dissolved in deionization
In water and ultrasound 15min keeps its evenly dispersed, obtains the aqueous solution of Ag/AgCl@ZIF-8.
The quality percentage of Ag/AgCl contains in Ag/AgCl@ZIF-8 used in step S200 in one of the embodiments,
Amount is 20%~50%.Further, it is found through experiments that, the mass percentage of Ag/AgCl in above-mentioned Ag/AgCl@ZIF-8
Preferably 35%.
Step S300: the wet sample of photocatalysis sponge in drying steps S200 obtains the photocatalysis for removing algae and water
Sponge.
Step S300 is specifically, the wet sample of photocatalysis sponge to be heat-treated 12h, phase at 90 DEG C to make moisture evaporation
Between, every several minutes by sponge turn-over until the moisture on its surface evaporates, to prevent catalyst deposit in certain side of sponge.
It should be noted that the step of step S100 is modified sponge, to prepare the light for removing algae and water
It is catalyzed step preferred when sponge.Modified sponge has better load effect to Ag/AgCl@ZIF-8.
As shown in figure 3, the photocatalysis sponge for being used to remove algae and water of an embodiment, including modified sponge and absorption
Ag/AgCl@ZIF-8 on the modified sponge.Wherein, in the photocatalysis sponge for removing algae and water, a part
Ag/AgCl@ZIF-8 be adsorbed in the hole of modified sponge, the Ag/AgCl@ZIF-8 of another part is adsorbed in modified sponge
On outer surface.
Current photochemical catalyst system is essentially suspension system, the homogeneous pollutant being only applicable in water body, uncomfortable symphysis
It is longer than the algae of water surface, and current photochemical catalyst is substantially powdered, is not easily recycled in the application, it may be to ring
Border generates secondary pollution.And it is above-mentioned using sponge loaded composite photocatalysis agent Ag/AgCl@ZIF-8 be prepared for removing
The photocatalysis sponge of algae and water, since the buoyancy of sponge can float on the water surface of generation wawter bloom, and Ag/AgCl
ZIF-8 can directly utilize photon energy, so as to efficiently dispose the algae of water surface；And utilize the above method
The photocatalysis sponge for removing algae and water being prepared is crumb structure, is easy recovery processing.
The above-mentioned photocatalysis sponge for removing algae and water can be used in administering wawter bloom.Further, wawter bloom is indigo plant
Algae wawter bloom.
The above-mentioned photocatalysis sponge for removing algae and water floats on water surface, Ke Yizhi based on the buoyancy of sponge
It connects using photon energy, to improve photochemical catalyst to the utilization rate of photon；Buoyancy based on sponge floats on water surface,
It can directly be contacted in the algae that wawter bloom occurs, remove algae efficiency to improve；And the crumb structure based on sponge, is convenient for
It recycles.
The following are specific embodiment parts:
In the examples below, such as without special explanation, then without containing other unknown in addition to inevitable impurity
The component really pointed out；Water used in preparation process as solvent action is all deionized water.
Embodiment 1
(1) preparation of ZIF-8
By 2.348g Zn (NO3)2·6H2O and 5.192g 2-methylimidazole is dissolved in respectively in 160mL anhydrous methanol must be molten
Liquid A and solution B, are quickly poured into solution A in solution B after completely dissolution, persistently stir 2h at room temperature.After stirring
Centrifugation removal supernatant washs precipitating 3 times to remove extra 2-methylimidazole with dehydrated alcohol, the milky white precipitate that will be obtained
In 70 DEG C of oven drying 12h, ZIF-8 is obtained.
(2) preparation of Ag/AgCl@ZIF-8
0.2g ZIF-8 is taken to be dissolved in 12.9mLAgNO3Solution (53.7mM, wherein AgNO3The solvent of solution is volume ratio 1
: 6 deionized water and dehydrated alcohol) in, 3h is stirred at room temperature.98mL is added dropwise in above-mentioned solution in 20min
NaCl (0.03g) solution (wherein, the solvent of NaCl solution be volume ratio 1: 6 deionized water and dehydrated alcohol) in, stirring
Bluish violet product is obtained after 10h, is washed with deionized after centrifugation three times to remove excess NaCl.By obtained product at 70 DEG C
Lower dry 12h obtains Ag/AgCl@ZIF-8, at this time Ag/AgCl accounting 35% in Ag/AgCl@ZIF-8.
(3) preparation of modified sponge
2 clean sponges of pretreatment are taken to be immersed in the neopelex (SDS) that 50mL concentration is 3.0g/L molten
In liquid, being placed in oscillation on shaking table comes into full contact with it.Sponge is taken out after 30min, is washed away with deionized water immersion more on sponge
Remaining SDS, and be put into baking oven and dry, obtain modified sponge.
(4) for removing the preparation of the photocatalysis sponge of algae and water
It weighs 0.125g Ag/AgCl@ZIF-8 and is dissolved in 50mL deionized water simultaneously ultrasound 15min, keep its evenly dispersed, obtain
The Ag/AgCl@ZIF-8 aqueous solution for being 2.5g/L to concentration；
It takes 2 above-mentioned modified sponges to be immersed in Ag/AgCl ZIF-8 aqueous solution, takes out sea after being placed in shaking table oscillation 2h
Silk floss is dried at 90 DEG C, during which every several minutes by sponge turn-over until its surface moisture evaporate, to prevent catalyst deposit
In sponge side；
After dry 12h, the photocatalysis sponge for being used to remove algae and water that load has Ag/AgCl@ZIF-8 is obtained.
Embodiment 2
(1) preparation of ZIF-8
By 2.348g Zn (NO3)2·6H2O and 5.192g 2-methylimidazole is dissolved in respectively in 160mL anhydrous methanol must be molten
Liquid A and solution B, are quickly poured into solution A in solution B after completely dissolution, persistently stir 2h at room temperature.After stirring
Centrifugation removal supernatant washs precipitating 3 times to remove extra 2-methylimidazole with dehydrated alcohol, the milky white precipitate that will be obtained
In 70 DEG C of oven drying 12h, ZIF-8 is obtained.
(2) preparation of Ag/AgCl@ZIF-8
0.2g ZIF-8 is taken to be dissolved in 3.3mL AgNO3Solution (53.7mM, wherein AgNO3The solvent of solution is volume ratio 1
: 6 deionized water and dehydrated alcohol) in, 3h is stirred at room temperature.98mL is added dropwise in above-mentioned solution in 20min
NaCl (0.03g) solution (wherein, the solvent of NaCl solution be volume ratio 1: 6 deionized water and dehydrated alcohol) in, stirring
Bluish violet product is obtained after 10h, is washed with deionized after centrifugation three times to remove excess NaCl.By obtained product at 70 DEG C
Lower dry 12h obtains Ag/AgCl@ZIF-8, at this time Ag/AgCl accounting 20% in Ag/AgCl@ZIF-8.
(3) preparation of modified sponge
2 clean sponges of pretreatment are taken to be immersed in the neopelex (SDS) that 50mL concentration is 3.0g/L molten
In liquid, being placed in oscillation on shaking table comes into full contact with it.Sponge is taken out after 30min, is washed away with deionized water immersion more on sponge
Remaining SDS, and be put into baking oven and dry, obtain modified sponge.
(4) for removing the preparation of the photocatalysis sponge of algae and water
It weighs 0.125g Ag/AgCl@ZIF-8 and is dissolved in 50mL deionized water simultaneously ultrasound 15min, keep its evenly dispersed, obtain
The Ag/AgCl@ZIF-8 aqueous solution for being 2.5g/L to concentration；
It takes 2 above-mentioned modified sponges to be immersed in Ag/AgCl ZIF-8 aqueous solution, takes out sea after being placed in shaking table oscillation 2h
Silk floss is dried at 90 DEG C, during which every several minutes by sponge turn-over until its surface moisture evaporate, to prevent catalyst deposit
In sponge side.
After dry 12h, the photocatalysis sponge for being used to remove algae and water that load has Ag/AgCl@ZIF-8 is obtained.
Embodiment 3
(1) preparation of ZIF-8
By 2.348g Zn (NO3)2·6H2O and 5.192g 2-methylimidazole is dissolved in respectively in 160mL anhydrous methanol must be molten
Liquid A and solution B, are quickly poured into solution A in solution B after completely dissolution, persistently stir 2h at room temperature.After stirring
Centrifugation removal supernatant washs precipitating 3 times to remove extra 2-methylimidazole with dehydrated alcohol, the milky white precipitate that will be obtained
In 70 DEG C of oven drying 12h, ZIF-8 is obtained.
(2) preparation of Ag/AgCl@ZIF-8
0.2g ZIF-8 is taken to be dissolved in 14mL AgNO3Solution (53.7mM, wherein AgNO3The solvent of solution is volume ratio 1:
6 deionized water and dehydrated alcohol) in, 3h is stirred at room temperature.Above-mentioned solution is added dropwise 98mL's in 20min
In NaCl (0.03g) solution (wherein, deionized water and dehydrated alcohol that the solvent of NaCl solution is volume ratio 1: 6), 10h is stirred
After obtain bluish violet product, be washed with deionized after centrifugation three times to remove excess NaCl.By obtained product at 70 DEG C
Dry 12h, obtains Ag/AgCl@ZIF-8, at this time Ag/AgCl accounting 50% in Ag/AgCl@ZIF-8.
(3) preparation of modified sponge
2 clean sponges of pretreatment are taken to be immersed in the neopelex (SDS) that 50mL concentration is 3.0g/L molten
In liquid, being placed in oscillation on shaking table comes into full contact with it.Sponge is taken out after 30min, is washed away with deionized water immersion more on sponge
Remaining SDS, and be put into baking oven and dry, obtain modified sponge.
(4) for removing the preparation of the photocatalysis sponge of algae and water
It weighs 0.125g Ag/AgCl@ZIF-8 and is dissolved in 50mL deionized water simultaneously ultrasound 15min, keep its evenly dispersed, obtain
The Ag/AgCl@ZIF-8 aqueous solution for being 2.5g/L to concentration；
It takes 2 above-mentioned modified sponges to be immersed in Ag/AgCl ZIF-8 aqueous solution, takes out sea after being placed in shaking table oscillation 2h
Silk floss is dried at 90 DEG C, during which every several minutes by sponge turn-over until its surface moisture evaporate, to prevent catalyst deposit
In sponge side.
After dry 12h, the photocatalysis sponge for being used to remove algae and water that load has Ag/AgCl@ZIF-8 is obtained.
Comparative example 1
As a control group, used sponge is non-modified processing and does not have loaded Ag/AgCl@ZIF-8 comparative example 1
General sponge.
Except algae is tested
The photocatalysis sponge for removing algae and water for taking 1 embodiment 1 to be prepared adds to (the choosing of 100mL algae solution
Use microcystic aeruginosa as test algae, initial algae density is 6.48 × 106Cells/mL, algae when being equivalent to Blue-green Algae Fast Growth are close
Degree) in, it is anti-to be placed in progress photocatalysis in photo catalysis reactor (filtering off wavelength < 420nm ultraviolet light using edge filter)
Answer 6h.The Chlorophyll-a Content in algae is measured by sampling every 1h.
Embodiment 2 and embodiment 3 and comparative example 1 for removing the photocatalysis sponge or sponge of algae and water, also with
The photocatalysis sponge for removing algae and water of embodiment 1 is cooked similarly except algae is tested.
Test result as shown in Fig. 1 shows: after 6h reacts, embodiment 1 is preparation-obtained for going to remove water
The photocatalysis sponge of body algae except algae effect it is best, chlorophyll a removal rate is up to 93.1%；Embodiment 2 and embodiment 3 are made
Standby obtained photocatalysis sponge except algae effect it is slightly poor, chlorophyll a removal rate is respectively 76.3% and 75.8%；And comparative example 1
In, chlorophyll a removal rate only has 17.3%, main to be removed by sponge to the suction-operated of frustule.It follows that embodiment
Photocatalysis sponge for removing algae and water is prepared has an excellent algae removal efficiency, and embodiment 1 is prepared
The photocatalysis sponge for removing algae and water of 35%Ag/AgCl doping has more excellent algae removal efficiency.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of for removing the preparation method of the photocatalysis sponge of algae and water, which comprises the steps of:
Using the aqueous solution soaking sponge of Ag/AgCl@ZIF-8, the wet sample of photocatalysis sponge is obtained；
The dry wet sample of photocatalysis sponge, obtains the photocatalysis sponge for removing algae and water.
2. according to claim 1 for removing the preparation method of the photocatalysis sponge of algae and water, which is characterized in that
It further include impregnate to the sponge using surfactant solution changing before described the step of obtaining photocatalysis sponge wet sample
The step of property.
3. according to claim 2 for removing the preparation method of the photocatalysis sponge of algae and water, which is characterized in that institute
It states and includes: using the step that surfactant impregnate modification to the sponge
The sponge is impregnated using surfactant solution；
The sponge is taken out, the surfactant solution extra on the sponge is disposed；
The dry sponge, obtains modified sponge.
4. the preparation method of photocatalysis sponge according to claim 2, which is characterized in that the surfactant solution is
Neopelex solution.
5. according to claim 1 for removing the preparation method of the photocatalysis sponge of algae and water, which is characterized in that institute
Ag/AgCl@ZIF-8 is stated to need to use AgNO in synthesis3Solution and NaCl solution, the AgNO3The solvent of solution is deionization
The volume ratio of water and dehydrated alcohol, the deionized water and the dehydrated alcohol is 1: 3~1: 6；The solvent of the NaCl solution
For deionized water and dehydrated alcohol, the volume ratio of the deionized water and the dehydrated alcohol is 1: 3~1: 6.
6. according to claim 5 for removing the preparation method of the photocatalysis sponge of algae and water, which is characterized in that institute
The mass percentage for stating Ag/AgCl in Ag/AgCl@ZIF-8 is 20%~50%.
7. according to claim 6 for removing the preparation method of the photocatalysis sponge of algae and water, which is characterized in that institute
The mass percentage for stating Ag/AgCl in Ag/AgCl@ZIF-8 is 35%.
8. a kind of for removing the photocatalysis sponge of algae and water, which is characterized in that the light for removing algae and water is urged
Changing sponge includes modified sponge and the Ag/AgCl@ZIF-8 being adsorbed on the modified sponge.
9. the photocatalysis sponge according to any one of claims 8 for removing algae and water is in the application administered in wawter bloom.
10. application according to claim 9, which is characterized in that the wawter bloom is cyanobacterial bloom.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111389425A (en) * | 2020-05-15 | 2020-07-10 | 福州大学 | Perovskite photocatalytic material for removing algae in water body and preparation method thereof |
| CN113856756A (en) * | 2021-10-15 | 2021-12-31 | 暨南大学 | Ag/TiO2Preparation method and application of composite modified sponge |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701664A (en) * | 2019-02-11 | 2019-05-03 | 盐城师范学院 | A kind of Ag/AgBr@ZIF-8 composite photo-catalyst and its preparation method and application |
| CN211988673U (en) * | 2019-07-18 | 2020-11-24 | 深圳市深港产学研环保工程技术股份有限公司 | Photocatalytic sponge for removing algae in water body |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109701664A (en) * | 2019-02-11 | 2019-05-03 | 盐城师范学院 | A kind of Ag/AgBr@ZIF-8 composite photo-catalyst and its preparation method and application |
| CN211988673U (en) * | 2019-07-18 | 2020-11-24 | 深圳市深港产学研环保工程技术股份有限公司 | Photocatalytic sponge for removing algae in water body |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111389425A (en) * | 2020-05-15 | 2020-07-10 | 福州大学 | Perovskite photocatalytic material for removing algae in water body and preparation method thereof |
| CN111389425B (en) * | 2020-05-15 | 2022-08-12 | 福州大学 | Perovskite photocatalytic material for removing algae in water body and preparation method thereof |
| CN113856756A (en) * | 2021-10-15 | 2021-12-31 | 暨南大学 | Ag/TiO2Preparation method and application of composite modified sponge |
| CN113856756B (en) * | 2021-10-15 | 2023-11-24 | 暨南大学 | Ag/TiO 2 Preparation method and application of composite modified sponge |
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