CN117361732A - Multi-thorn-shaped magnetic micro-nano robot for sewage treatment and preparation method thereof - Google Patents
Multi-thorn-shaped magnetic micro-nano robot for sewage treatment and preparation method thereof Download PDFInfo
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- CN117361732A CN117361732A CN202311310556.6A CN202311310556A CN117361732A CN 117361732 A CN117361732 A CN 117361732A CN 202311310556 A CN202311310556 A CN 202311310556A CN 117361732 A CN117361732 A CN 117361732A
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- 238000011282 treatment Methods 0.000 title claims abstract description 60
- 239000010865 sewage Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 53
- 239000011248 coating agent Substances 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 24
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 241000208818 Helianthus Species 0.000 claims abstract description 20
- 235000003222 Helianthus annuus Nutrition 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000005389 magnetism Effects 0.000 claims 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 12
- 231100000719 pollutant Toxicity 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 9
- -1 iron ions Chemical class 0.000 description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 238000011084 recovery Methods 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XNCMOUSLNOHBKY-UHFFFAOYSA-H iron(3+);trisulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XNCMOUSLNOHBKY-UHFFFAOYSA-H 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
- B25J—MANIPULATORS; CHAMBERS PROVIDED WITH MANIPULATION DEVICES
- B25J19/00—Accessories fitted to manipulators, e.g. for monitoring, for viewing; Safety devices combined with or specially adapted for use in connection with manipulators
- B25J19/007—Means or methods for designing or fabricating manipulators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
- B25J—MANIPULATORS; CHAMBERS PROVIDED WITH MANIPULATION DEVICES
- B25J7/00—Micromanipulators
-
- 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
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Robotics (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to the field of micro-nano robots, in particular to a multi-thorn magnetic micro-nano robot for sewage treatment and a preparation method thereof, wherein the method comprises the following steps: s1: processing the extracted sunflower pollen to form pollen particles with uniform size; s2: purifying pollen particles, cleaning and drying; s3: coating ferroferric oxide on the surface of pollen particles by a codeposition method to form a magnetic coating; s4: performing high-temperature carbonization treatment on the pollen particles coated with the ferroferric oxide coating to obtain the multi-thorn-shaped magnetic micro-nano robot for removing pollen; s5: applying polypyrrole to the magnetic multi-thorn particles by an in-situ oxidation polymerization method to obtain the multi-thorn magnetic micro-nano robot with the photo-thermal material coating; can realize the fixed-point degradation of pollutants, is convenient to recycle, and effectively prevents secondary pollution.
Description
Technical Field
The invention relates to the field of micro-nano robots, in particular to a multi-thorn magnetic micro-nano robot for sewage treatment and a preparation method thereof.
Background
Along with the development of industrialization, water pollution becomes an increasingly serious problem; in order to maintain the environment and human health, it is necessary to perform the treatment of contaminants by physical or chemical means; however, the efficiency of these treatments is limited by diffusion, and external stirring is required to increase the rate; in addition, the conventional physical or chemical treatment method is difficult to effectively remove the enriched pollutants or degradation products, and secondary pollution is easy to cause.
The micro-nano robot can have a profound effect on the environment; in the field of sewage treatment, micro-nano robots exhibit unique advantages, on the one hand, the micro-nano robots with the sizes of micrometers or nanometers have natural advantages, such as higher specific surface area, higher catalytic efficiency and the like; on the other hand, the micro-nano robot has active mobility under the drive of a non-contact external field, and the continuous motion of the micro-scale object can be realized without external stirring, so that the efficiency is improved, the cleaning time is shortened, and the micro-nano robot is more convenient and efficient in the aspect of degrading pollutants in sewage;
the sewage treatment mode which is most commonly used utilizes the self adsorption and catalytic oxidation effects of the micro-nano robot; when sewage treatment is carried out, a small amount of sewage treatment micro-nano robot and hydrogen peroxide solution are added into sewage, the micro-nano robot releases specific ions (such as iron ions) to catalyze and decompose hydrogen peroxide through Fenton reaction, and the released oxygen pushes the micro-nano robot to move, so that generated hydroxyl free radicals (OH) have super-strong oxidizing property, and macromolecular pollutants in the sewage are oxidized and degraded into pollution-free micromolecules, so that the purification effect is achieved.
Disclosure of Invention
The invention aims to provide a multi-thorn magnetic micro-nano robot for sewage treatment and a preparation method thereof, which can realize fixed-point pollutant degradation, facilitate recovery and effectively prevent secondary pollution.
The aim of the invention is achieved by the following technical scheme:
the multi-thorn-shaped magnetic micro-nano robot for sewage treatment comprises a multi-thorn-shaped micro-nano robot and a magnetic coating coated on the multi-thorn-shaped micro-nano robot, wherein the magnetic coating is coated with a photo-thermal material coating;
the multi-thorn-shaped micro-nano robot is obtained by performing high-temperature carbonization treatment on pollen particles coated with a magnetic coating to remove pollen, wherein the pollen particles are prepared based on sunflower pollen;
the magnetic coating is a ferroferric oxide layer;
the photo-thermal material coating is a polypyrrole layer;
a preparation method of a multi-thorn magnetic micro-nano robot for sewage treatment comprises the following steps:
s1: processing the extracted sunflower pollen to form pollen particles with uniform size;
s2: purifying pollen particles, cleaning and drying;
s3: coating ferroferric oxide on the surface of pollen particles by a codeposition method to form a magnetic coating;
s4: performing high-temperature carbonization treatment on the pollen particles coated with the ferroferric oxide coating to obtain the multi-thorn-shaped magnetic micro-nano robot for removing pollen;
s5: applying polypyrrole to the magnetic multi-thorn particles by an in-situ oxidation polymerization method to obtain the multi-thorn magnetic micro-nano robot with the photo-thermal material coating;
the process of processing the sunflower pollen into the pollen particles with uniform size in the S1 comprises the following steps: grinding sun flower pollen after sun flower pollen is extracted to obtain pollen particles, carrying out ultrasonic dispersion treatment on the ground pollen particles, and obtaining pollen particles with uniform size by using a step-by-step filtration method;
in the step S2, the purification process of the pollen particles comprises two soaking treatments;
and (3) performing primary soaking treatment: immersing the pollen particles in a mixed solution of chloroform and methanol for 24 hours to dissolve organic medium doped in the pollen particles, and then vacuum drying the pollen particles for 12 hours at 60 ℃, wherein the volume ratio of the mixed solution of chloroform and methanol is 3:1, a step of;
and (3) soaking for the second time: soaking in 1mol/L hydrochloric acid solution for 1h, removing residual organic matters, and then washing with deionized water for 3 times to obtain clean and dispersed pollen particles;
in S3, the co-deposition method includes the following steps:
s31: 100mg of the prepared dried pollen particles were dispersed in 150mL of deionized water, and 59mg of ferrous chloride hexahydrate and 60mg of ferrous sulfate heptahydrate were added to the dispersion;
s32: stirring the obtained suspension in a water bath at 50 ℃ for 1 hour under the protection of nitrogen, dropwise adding an ammonia solution into the dispersion system to enable the pH value of the dispersion system to reach 8-9, and stirring the mixture for 0.5 hour after setting the temperature to 55 ℃ in the water bath;
s33: after solid deposition in the dispersion system, separating black deposition by using a permanent magnet, flushing powder with deionized water for 3 times, and drying at 60 ℃ for 12.0 hours;
s34: repeating the steps S31 to S33 to build up the coating of the ferroferric oxide with different thickness;
the high-temperature carbonization treatment in the step S4 comprises the following steps: heating pollen particles coated with a ferroferric oxide layer to a peak temperature of 600 ℃ at a speed of 0.5 ℃/min under the condition of 0.5Pa of vacuum degree, then keeping the temperature for 4 hours, and extracting after cooling to obtain the biomass-free multi-thorn-shaped magnetic micro-nano robot;
the in-situ oxidation polymerization method in S5 comprises the following steps:
s51: dispersing 10mg of the magnetic spiny particles into 10ml of deionized water in which 30mg of polyvinyl alcohol and 10mg of sodium dodecyl benzene sulfonate are dissolved, and ultrasonically dispersing the obtained suspension at room temperature for 20min;
s52: after stirring for 2h, 40. Mu.L of pyrrole monomer is added into the dispersion system, and the mixture is stirred for 40min;
s53: then dropwise adding an aqueous solution containing 40mg of ferrous chloride hexahydrate into the system to be dispersed;
s54: after reacting for 12 hours at room temperature, separating black deposition by using a permanent magnet, and flushing powder with deionized water for 3 times;
s55: drying for 12h at room temperature to obtain the multi-thorn magnetic micro-robot for sewage treatment.
The beneficial effects of the invention are as follows:
the magnetic coating is coated on the outer surface of the multi-thorn-shaped micro-nano robot through a coprecipitation process to realize magnetic driving, the motion state of the multi-thorn-shaped micro-nano robot is controlled, the fixed-point pollutant degradation can be realized, the pollutant is recovered, the secondary pollution is prevented, the ferroferric oxide coating releases iron ions, and the effect of purifying sewage is realized by decomposing hydrogen peroxide and releasing hydroxyl free radicals through Fenton reaction catalysis;
the multi-thorn-shaped structure is obtained after high-temperature carbonization treatment, so that the multi-thorn-shaped magnetic micro-nano robot has higher specific surface area, and has higher catalytic efficiency;
the polypyrrole photo-thermal conversion material coating is coated on the surface of the multi-thorn magnetic micro-nano robot through an in-situ oxidation polymerization process, the polypyrrole has good photo-thermal effect, the ferroferric oxide can be promoted to release iron ions under the condition of illumination, and the efficiency of the multi-thorn magnetic micro-nano robot for catalyzing and decomposing hydrogen peroxide to treat sewage is improved.
Drawings
The invention will be described in further detail with reference to the accompanying drawings and detailed description.
FIG. 1 is a schematic diagram of a preparation flow of a multi-thorn magnetic micro-nano robot for sewage treatment;
FIG. 2 is a schematic diagram of MB solution color change of the multi-thorn magnetic micro-nano robot for sewage after sewage treatment;
FIG. 3 is a schematic view of MB ultraviolet absorption spectrum change of the multi-thorn magnetic micro-nano robot for sewage after sewage treatment;
fig. 4 is a schematic diagram of a magnetic control recovery process of the multi-thorn magnetic micro-nano robot after sewage treatment.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings.
As shown in fig. 1 to 4, in order to achieve the technical effects of "can realize fixed-point degradation of pollutants, and convenient recovery, and effectively prevent secondary pollution", the structure and function of a multi-thorn magnetic micro-nano robot for sewage treatment are described in detail below;
the multi-thorn-shaped magnetic micro-nano robot for sewage treatment comprises a multi-thorn-shaped micro-nano robot, wherein the multi-thorn-shaped micro-nano robot is prepared based on pollen particles, the pollen particles are prepared based on sunflower pollen, and the reasons for using the sunflower pollen mainly have two points, namely, the preparation process of the sunflower pollen is mature, and the finished sunflower pollen is easy to obtain; secondly, the multi-thorn shape of the sunflower pollen is obvious and the structural stability is high, so that the multi-thorn shape of the multi-thorn magnetic micro-nano robot directly obtained after the magnetic coating is applied to the surface of the sunflower pollen serving as a substrate is excellent and uniform;
the sunflower pollen particles are uniformly distributed on the surface and have a regular multi-thorn structure, and the diameter of the sunflower pollen particles is about 30 mu m. Then, fe grows on the pollen surface by coprecipitation 3 O 4 A layer imparting a magnetic response thereto. The overall size of the pollen remains unchanged and the thorn structure of the pollen is preserved. Then, the pollen is coated with Fe 3 O 4 Carbonizing the layer to obtain biomass-free multi-thorn Fe 3 O 4 The template size was reduced to about 16 μm. The uniformly distributed multi-thorn-shaped surface morphology is maintained, but the multi-thorn-shaped structure becomes flat and wrinkled, the specific surface area of the particles is further increased, and the contact and removal efficiency of the particles on pollutants in water is improved;
the multi-thorn-shaped micro-nano robot is coated with a magnetic coating, the magnetic coating is coated with a photo-thermal material coating, as shown in figure 1, pollen particles with multi-thorn-shaped structures are respectively arranged from left to right, then pollen particles with the magnetic coating are obtained through a coprecipitation method, and then the independent multi-thorn-shaped magnetic micro-nano robot is obtained through high-temperature carbonization, and the photo-thermal conversion material coating is coated on the surface of the multi-thorn-shaped magnetic micro-nano robot;
the pollen particles are prepared based on sunflower pollen, have a multi-thorn-shaped structure, and the multi-thorn-shaped structure can remarkably increase the specific surface area of the multi-thorn-shaped magnetic micro-nano robot, enhance the contact rate with pollutants and improve the removal effect;
the magnetic coating is a ferroferric oxide layer, and can release iron ions in the water treatment process, so that the magnetic coating has good magnetic response performance, is favorable for later recovery and does not cause secondary pollution;
the photo-thermal material coating is a polypyrrole layer, has good photo-thermal performance, and can promote release of iron ions under the irradiation of near infrared light;
a preparation method of a multi-thorn magnetic micro-nano robot for sewage treatment comprises the following steps:
extracting and crushing: during pollen extraction and cleaning, firstly, large pollen particles are crushed, dispersed by ultrasonic treatment, and pollen particles with uniform size are obtained by a step-by-step filtration method;
further, cleaning is performed: immersing in chloroform and methanol solution for 24h to remove pollen sheath. Wherein the volume ratio of chloroform to methanol is 3 to 1, and the mixture is dried in vacuum for 12 hours at 60 ℃. A second soaking treatment, namely soaking the raw materials in 1M hydrochloric acid for 1h to remove residual inorganic substances, flushing the raw materials with deionized water for 3 times, and vacuum drying the raw materials at room temperature for 5min;
further, a coprecipitation process is performed to coat the magnetic layer: as shown in fig. 1, 100mg of the prepared dried pollen grains were dispersed in 150mL of deionized water, and 59mg of ferric chloride hexahydrate and 60mg of ferric sulfate heptahydrate were added to the dispersion. The resulting suspension was stirred in a 50℃water bath under nitrogen protection for 1 hour, the ammonia solution was added dropwise to the dispersion to bring the pH of the dispersion to 8 to 9, and the mixture was stirred for a further 0.5 hour after setting the temperature to 55℃in the water bath. After the solids in the dispersion precipitated, the black precipitate was separated by permanent magnets and the powder was rinsed 3 times with deionized water, the particles were vacuum filtered and dried by drying at 60 ℃ for 12.0 hours. By repeating the above process, various thicknesses of the coating containing ferroferric oxide can be established.
Further, high temperature carbonization is performed: the pollen grains coated with the ferroferric oxide layer were heated to a peak temperature of 600 c at a rate of 0.5 c/min under a vacuum of 0.5Pa and then maintained at that temperature for 4 hours. And then cooling to room temperature and extracting to obtain the biomass-free magnetic multi-thorn-shaped micro-nano robot. The independent magnetic multi-thorn micro-nano robot is obtained through high-temperature carbonization treatment, such as the part shown in fig. 1. The magnetic coating is ferroferric oxide, can release ferric ions during sewage purification, has stronger magnetic response performance, and is favorable for recovery.
Further, coating the photo-thermal conversion material coating by adopting an in-situ oxidation polymerization process: as shown in fig. 1, 10mg of the prepared spiny magnetic particles were dispersed in 10ml of deionized water in which 30mg of polyvinyl alcohol and 10mg of sodium dodecylbenzenesulfonate were dissolved, and the resulting suspension was ultrasonically dispersed at room temperature for 20min. After stirring for 2h, 40. Mu.L of pyrrole monomer was added to the above dispersion and the mixture was stirred for a further 40min. Then, an aqueous solution containing 40mg of ferric chloride hexahydrate was dropwise added to the above-described dispersion. After 12h reaction at room temperature, the black precipitate was separated by permanent magnet and the powder was rinsed 3 times with deionized water. Drying at room temperature for 12.0 hours to obtain the multi-thorn-shaped magnetic micro-nano robot for sewage treatment. The coating of the photothermal conversion material is preferably polypyrrole, which is beneficial to accelerating the release of iron ions in the magnetic layer through the photothermal effect.
The micro-nano robot is put into the sewage polluted by the organic matters to be treated and then added with H in the degradation operation process of the organic pollutants based on the micro-nano robot 2 O 2 To 1%, adding a multi-thorn-shaped micro-robot, and processing for 5-15 minutes under the combined drive of ultrasonic and near infrared illumination. After the treatment, the strong magnet is used for adsorbing, gathering and separating the micro-robot from water.
In order that the invention may be more readily understood, the following examples are provided for the purpose of further illustration and are not intended to limit the scope of the invention;
the purification efficiency of sewage is studied by taking Methylene Blue (MB) as a model, 1.5ml of MB solution with the mass concentration of 10mg/L is taken, hydrogen peroxide solution is added to 1%, 200ug of the multi-thorn-shaped magnetic micro-nano robot for sewage treatment is added, and iron ions released by a magnetic layer promote the decomposition of hydrogen peroxide through Fenton reaction to release hydroxyl free radicals (OH) and oxygen. Under the pushing of oxygen and ultrasonic waves, the micro-nano robot moves, the contact rate of macromolecular pollutants and the micro-nano robot is increased, and generated hydroxyl radicals (OH) have strong oxidability and degrade the macromolecular pollutants through oxidation reaction. After 5min, the micro-nano robot for sewage treatment is adsorbed by the permanent magnet.
As shown in fig. 2, MB was removed after 5min under different conditions with and without micro-nano robots, with the addition of ferroferric oxide spherical particles, and with micro-nano robots and ultrasound driving or not. Obviously, compared with spherical ferroferric oxide particles, the multi-thorn-shaped magnetic micro-nano robot has stronger MB removing capability.
As shown in FIG. 3, the result of FIG. 2 was confirmed by the ultraviolet absorption spectrum of MB solution after 5min of sewage treatment.
As shown in FIG. 4, the multi-thorn-shaped magnetic micro-nano robot for sewage treatment can be well separated from the solution under the condition of an externally applied magnetic field, and the result shows that the magnetic micro-nano robot has good recoverability, avoids secondary pollution to water and has wide application prospect in actual sewage treatment.
The multi-thorn-shaped magnetic micro-nano robot for sewage treatment is used by being mixed with hydrogen peroxide, the characteristic of large specific surface area of the multi-thorn-shaped micro-nano robot is utilized, the efficiency of catalyzing hydrogen peroxide to decompose by virtue of Fenton reaction of iron ions is increased, and meanwhile, the photo-thermal conversion coating on the surface of the micro-nano robot can promote the release of iron ions of ferroferric oxide on the magnetic coating through photo-thermal reaction. The multi-thorn magnetic micro-nano robot for sewage treatment has strong magnetic response performance, good recoverability, can avoid secondary pollution to water body, and has application value in sewage treatment.
The above-described embodiments are subjected to various variations and modifications without departing from the technical ideas of the present application, and all such variations and modifications are intended to fall within the scope of the present application.
Claims (10)
1. The utility model provides a sewage treatment's thorny form magnetism micro-nano robot, includes thorny form micro-nano robot and coats the magnetism coating on thorny form micro-nano robot, its characterized in that: the magnetic coating is coated with a photo-thermal material coating.
2. The multi-thorn-shaped magnetic micro-nano robot for sewage treatment according to claim 1, wherein: the multi-thorn-shaped micro-nano robot is obtained by performing high-temperature carbonization treatment on pollen particles coated with a magnetic coating to remove pollen, and the pollen particles are prepared based on sunflower pollen.
3. The multi-thorn-shaped magnetic micro-nano robot for sewage treatment according to claim 1, wherein: the magnetic coating is a ferroferric oxide layer.
4. The multi-thorn-shaped magnetic micro-nano robot for sewage treatment according to claim 1, wherein: the photo-thermal material coating is a polypyrrole layer.
5. A preparation method of a multi-thorn magnetic micro-nano robot for sewage treatment is characterized by comprising the following steps: the method comprises the following steps:
s1: processing the extracted sunflower pollen to form pollen particles with uniform size;
s2: purifying pollen particles, cleaning and drying;
s3: coating ferroferric oxide on the surface of pollen particles by a codeposition method to form a magnetic coating;
s4: performing high-temperature carbonization treatment on the pollen particles coated with the ferroferric oxide coating to obtain the multi-thorn-shaped magnetic micro-nano robot for removing pollen;
s5: and applying polypyrrole to the magnetic multi-thorn-shaped micro-nano robot by using an in-situ oxidation polymerization method to obtain the multi-thorn-shaped magnetic micro-nano robot with the photo-thermal material coating.
6. The method for preparing the multi-thorn-shaped magnetic micro-nano robot for sewage treatment according to claim 6, which is characterized in that: the process of processing the sunflower pollen into the pollen particles with uniform size in the S1 comprises the following steps: grinding sunflower pollen after extracting the sunflower pollen to obtain pollen particles, performing ultrasonic dispersion treatment on the ground pollen particles, and obtaining the pollen particles with uniform size by using a step-by-step filtration method.
7. The method for preparing the multi-thorn-shaped magnetic micro-nano robot for sewage treatment according to claim 6, which is characterized in that: in the step S2, the purification process of the pollen particles comprises two soaking treatments;
and (3) performing primary soaking treatment: immersing pollen particles in chloroform and methanol solution for 24 hours, and then drying the pollen particles in vacuum at 60 ℃ for 12 hours, wherein the volume ratio of the chloroform to the methanol solution is 3:1, a step of;
and (3) soaking for the second time: soaking in 1mol/L hydrochloric acid solution for 1h, and then washing with deionized water for 3 times.
8. The method for preparing the multi-thorn-shaped magnetic micro-nano robot for sewage treatment according to claim 6, which is characterized in that: in S3, the co-deposition method includes the following steps:
s31: 100mg of the prepared dried pollen particles were dispersed in 150mL of deionized water, and 59mg of ferrous chloride hexahydrate and 60mg of ferrous sulfate heptahydrate were added to the dispersion;
s32: stirring the obtained suspension in a water bath at 50 ℃ for 1 hour under the protection of nitrogen, dropwise adding an ammonia solution into the dispersion system to enable the pH value of the dispersion system to reach 8-9, and stirring the mixture for 0.5 hour after setting the temperature to 55 ℃ in the water bath;
s33: after solid deposition in the dispersion system, separating black deposition by using a permanent magnet, flushing powder with deionized water for 3 times, and drying at 60 ℃ for 12.0 hours;
s34: steps S31 to S33 are repeated to build up a coating of ferroferric oxide of different thickness.
9. The method for preparing the multi-thorn-shaped magnetic micro-nano robot for sewage treatment according to claim 6, which is characterized in that: the high-temperature carbonization treatment in the step S4 comprises the following steps: and (3) heating the pollen particles coated with the ferroferric oxide layer to the peak temperature of 600 ℃ at the speed of 0.5 ℃/min under the condition of 0.5Pa of vacuum degree, then keeping the temperature for 4 hours, and cooling and extracting to obtain the biomass-free multi-thorn-shaped magnetic micro-nano robot.
10. The method for preparing the multi-thorn-shaped magnetic micro-nano robot for sewage treatment according to claim 6, which is characterized in that: the in-situ oxidation polymerization method in S5 comprises the following steps:
s51: dispersing 10mg of the magnetic spiny particles into 10ml of deionized water in which 30mg of polyvinyl alcohol and 10mg of sodium dodecyl benzene sulfonate are dissolved, and ultrasonically dispersing the obtained suspension at room temperature for 20min;
s52: after stirring for 2h, 40. Mu.L of pyrrole monomer is added into the dispersion system, and the mixture is stirred for 40min;
s53: then dropwise adding an aqueous solution containing 40mg of ferrous chloride hexahydrate into the system to be dispersed;
s54: after reacting for 12 hours at room temperature, separating black deposition by using a permanent magnet, and flushing powder with deionized water for 3 times;
s55: drying for 12h at room temperature to obtain the multi-thorn magnetic micro-robot for sewage treatment.
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