CN111558364A - Sn (tin)3O4-TiO2Heterojunction magnetic photocatalytic composite adsorption material and preparation method thereof - Google Patents
Sn (tin)3O4-TiO2Heterojunction magnetic photocatalytic composite adsorption material and preparation method thereof Download PDFInfo
- Publication number
- CN111558364A CN111558364A CN202010462743.6A CN202010462743A CN111558364A CN 111558364 A CN111558364 A CN 111558364A CN 202010462743 A CN202010462743 A CN 202010462743A CN 111558364 A CN111558364 A CN 111558364A
- Authority
- CN
- China
- Prior art keywords
- solution
- heterojunction
- tio
- magnetic
- heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 84
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 37
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920001661 Chitosan Polymers 0.000 claims abstract description 19
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 12
- 230000005389 magnetism Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 117
- 238000010438 heat treatment Methods 0.000 claims description 85
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000002904 solvent Substances 0.000 claims description 49
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000012265 solid product Substances 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 13
- 239000001509 sodium citrate Substances 0.000 claims description 12
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 12
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 238000007146 photocatalysis Methods 0.000 claims description 8
- 229940015043 glyoxal Drugs 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 14
- 238000009210 therapy by ultrasound Methods 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 6
- 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 5
- 230000017525 heat dissipation Effects 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
Images
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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of photocatalytic degradation and discloses Sn3O4‑TiO2The heterojunction magnetic photocatalytic composite adsorbing material comprises the following formula raw materials: magnetic chitosan-graphene Ce doped porous Sn3O4、TiCl4. The one kind of Sn3O4‑TiO2Heterojunction magnetic photocatalytic composite adsorption material, doping of Ce to make Sn3O4The generated oxygen defects can capture photo-generated electrons, reduce the recombination rate of the photo-generated electrons and holes, and Sn3O4‑TiO2The heterojunction promotes the migration and transmission of photo-generated electrons and holes, the separation efficiency of the photo-generated electrons and the holes of the heterojunction is improved, the recombination of the photo-generated electrons and the holes is effectively inhibited, and the lanthanum-doped zinc-cobalt ferrite in the magnetic chitosan-graphene has excellent magnetism and can be used for treating Cu2+、Cd2+The heavy metal ions are magnetically adsorbed, hydroxyl and amino in the chitosan can be complexed with the metal ions, the adsorption effect of the photocatalytic composite adsorption material on the heavy metals and ions thereof is enhanced, and the composite adsorption material is recovered through an external magnetic field.
Description
Technical Field
The invention relates to the technical field of photocatalytic degradation, in particular to Sn3O4-TiO2A heterojunction magnetic photocatalytic composite adsorption material and a preparation method thereof.
Background
The total amount of water resources in China is rich, but the per-capita amount only accounts for one fourth of the per-capita in the world, which is one of the world water-poor countries, but the quality of natural water resources in China at present is continuously reduced, the water environment is continuously deteriorated, water shortage and accidents caused by pollution are continuously caused, so that adverse social effects and major economic losses are caused, water pollution is caused by reduction or loss of the use value of water caused by harmful chemical substances, such as acids, alkalis, oxides, heavy metal compounds and ions thereof, so as to pollute the environment; organic pollutants such as halogenated alkanes, phenols, organic dyes and the like are mainly sourced from untreated industrial wastewater, domestic sewage, agricultural sewage, industrial waste discarded beside rivers and domestic garbage.
The current main methods for treating wastewater and water pollution include physical adsorption and flocculation sedimentation, biological metabolism treatment and chemical treatment, the chemical treatment comprises oxidation reduction, neutralization, chemical precipitation and the like, the chemical photocatalysis is a novel high-efficiency wastewater treatment method, and the principle is that the photocatalyst has oxidation reduction capability under the condition of illumination, so that the photocatalyst and pollutants are decomposed into small molecules by oxidation reduction, addition and the like, and the current photocatalyst semiconductor material mainly comprises TiO2Semiconductor material, BiOCl semiconductor material, SnO2Semiconductor material transition metal sulfide, etc., wherein Sn3O4Is a good semiconductor material, has the characteristics of narrow band gap, quick photoresponse and the like, is a photocatalytic semiconductor material with great potential, but the current Sn3O4The visible light absorption wave band of the photocatalytic material is narrow, the capability of absorbing light radiation is not strong, simultaneously the generated photoproduction electrons and holes are easy to be compounded, the photocatalytic activity of the material is greatly reduced, and the current Sn is not strong3O4The photocatalytic material can only degrade organic pollutants through oxidation-reduction reaction, has no adsorption performance on heavy metal pollutants and ions thereof, and greatly reduces the sewage treatment capacity.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides Sn3O4-TiO2The heterojunction magnetic photocatalytic composite adsorbing material and the preparation method thereof solve the problem of Sn3O4The photocatalytic material has weak ability of absorbing light radiation, and the generated photoproduction electrons and holes are easy to be combined, and simultaneously the problem of Sn is solved3O4The photocatalytic material has no problem of adsorption property to heavy metal pollutants and ions thereof.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: sn (tin)3O4-TiO2The heterojunction magnetic photocatalytic composite adsorbing material comprises the following formula raw materials in parts by weight: 14-26 parts of magnetic chitosan-graphene and 50-58 parts of Ce-doped porous Sn3O424-28 parts of TiCl4。
Preferably, the preparation method of the magnetic chitosan-graphene comprises the following steps:
(1) adding absolute ethyl alcohol solvent and Co into a reaction bottle3O4、Fe2O3ZnO and La2O3Transferring the solution into a planet ball mill, performing ball milling for 6-10h at a revolution speed of 600-620rpm and a rotation speed of 120-150rpm until the materials completely pass through a 600-800-mesh sieve, placing the mixed product in a vacuum hot-pressing sintering furnace at a sintering pressure of 25-30MPa and a heating rate of 5-10 ℃/min, and maintaining the temperature at 880-900 DEG CCalcining for 2-3h, heating to 1100-.
(2) Adding 4-8% by mass of acetic acid solution into a reaction bottle, adding chitosan, carboxylated graphene and lanthanum-doped zinc-cobalt ferrite, placing the reaction bottle into an ultrasonic treatment instrument, heating to 60-70 ℃, carrying out ultrasonic dispersion treatment for 2-3h, adding a catalyst p-toluenesulfonic acid into the reaction bottle, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 130-, and preparing the obtained magnetic chitosan-graphene.
Preferably, said Co3O4、Fe2O3ZnO and La2O3The molar ratio of the substances is 0.6:0.4:0.01-0.1:1.9-1.99, and the chemical expression of the lanthanum-doped zinc-cobalt ferrite is Zn0.4Co0.6La0.01-0.1Fe1.9-1.99O4。
Preferably, the mass ratio of the chitosan, the carboxylated graphene, the lanthanum-doped zinc-cobalt ferrite and the p-toluenesulfonic acid is 5-6:1:4.5-5: 0.005-0.008.
Preferably, the Ce is doped with porous Sn3O4The preparation method comprises the following steps:
(1) adding NaOH solution with pH of 12-13 into a reaction bottle, and then adding SnCl2、CeCl3And sodium citrate, placing the reaction bottle in an ultrasonic treatment instrument, heating to 70-80 ℃, performing ultrasonic dispersion treatment for 1-2h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 160-170 ℃, reacting for 15-20h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ce-doped porous Sn3O4。
Preferably, the SnCl2、CeCl3The molar ratio of the sodium citrate to the sodium citrate is 30-40:12-15: 1.
Preferably, said Sn3O4-TiO2The preparation method of the heterojunction magnetic photocatalytic composite adsorbing material comprises the following steps:
(1) adding ethanol and propylene glycol solvent into a reaction bottle, wherein the volume ratio of the ethanol to the propylene glycol solvent is 1.5-2:1, and then adding 14-26 parts of magnetic chitosan-graphene and 50-58 parts of Ce-doped porous Sn3O4And 24-28 parts of TiCl4Heating the solution in a constant temperature water bath to 50-60 ℃, stirring at a constant speed for reaction for 15-20h, adding an acetone solvent into the solution, stirring for 6-10h, concentrating the solution under reduced pressure to remove the solvent, washing the solid product with distilled water, and fully drying to prepare Sn3O4-TiO2A heterojunction magnetic photocatalytic composite adsorption material.
Preferably, the constant temperature water bath includes the casing, and the upper end fixed mounting of casing has the fly leaf, and the observation window has been seted up to the side of casing, and the left upper end fixed mounting of fly leaf has control panel, and the last fixed surface of fly leaf installs the reaction chamber, and the inside fixed mounting of reaction chamber has the hot plate, and the movable mounting of hot plate has the pot body, and the upper surface of fly leaf just is located fixed mounting between two hot plates and has the fixed plate, and the last fixed surface of fly leaf has control button, the inside fixed mounting of casing has the louvre.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the one kind of Sn3O4-TiO2Hetero-junction magnetic photocatalytic composite adsorption material, Ce doped Sn3O4Partial Sn atom lattice is replaced, the forbidden bandwidth is reduced, and the distance between the valence band and the conduction band is shortened, so that the Sn is widened3O4Can absorb light in a wave band, enhances the utilization rate of the photocatalytic material to light energy, and enables Sn to be doped by Ce3O4A large number of oxygen defects are generated in Sn3O4Oxygen defect state generated at the bottom of the conduction band, photo-generated electrons in the valence band are excited to oxygen vacancy energy level and then jump to the conduction band, and holes are left in the valence band, so that the oxygen defect on the conduction band can capture the photo-generated electrons, the recombination rate of the photo-generated electrons and the holes is reduced, the photocatalytic activity of the material is enhanced, the atomic radius of Ce is larger, and the Ce is doped in Sn3O4A large amount of mesoporous structures are formed on the surface of the lead-free tin alloy, and Sn is increased3O4The specific surface area and the light radiation area, thereby enhancing the light responsiveness and the light energy absorption rate of the photocatalytic material.
The one kind of Sn3O4-TiO2Heterojunction magnetic photocatalytic composite adsorption material and Sn prepared by in-situ method3O4-TiO2Heterojunction, TiO2Has a very wide ultraviolet-visible light absorption band, improves the light absorption efficiency of the heterojunction, and when light is radiated onto the heterojunction, Sn is formed3O4The generated photo-generated electrons are from Sn3O4To TiO2On the conduction band of TiO2Generated holes migrate from Sn to Sn3O4In valence band, the migration and transmission of the photoproduction electrons and the holes are promoted, the separation efficiency of the heterojunction photoproduction electrons and the holes is improved, and the recombination of the photoproduction electrons and the holes is effectively inhibited, so that the performance of photocatalytic degradation of organic pollutants is enhanced.
The one kind of Sn3O4-TiO2A heterojunction magnetic photocatalytic composite adsorption material is prepared by loading Sn on a magnetic chitosan-graphene material with a large specific surface area3O4-TiO2The heterojunction forms a composite material, and Sn is avoided3O4-TiO2The heterojunction is poor in water dispersibility and aggregated into large particles, so that the phenomenon of reduction of photocatalytic active sites of the material is caused, and the zinc-cobalt ferrite in the magnetic chitosan-graphene is doped with lanthanum to form a cubic spinel structure, so that the lattice parameter and the crystallization rate of the crystal are increased, the magnetic conductivity of the cobalt ferrite is reduced, the lanthanum-doped zinc-cobalt ferrite shows excellent magnetism, and the magnetic material can be used for treating Cu in sewage2+、Cd2+The heavy metal ions are magnetically adsorbed, and a large amount of hydroxyl and amino in the chitosan can be complexed with the metal ions, so that the adsorption effect of the photocatalytic composite adsorption material on the heavy metals and the ions thereof is enhanced, the catalytic composite adsorption material has good magnetism, the composite adsorption material can be recovered through an external magnetic field, the use efficiency is improved, and the secondary pollution is avoided.
Drawings
FIG. 1 is a side view of the present invention;
FIG. 2 is a top view of the present invention;
FIG. 3 is a rear view of the present invention;
in the figure: 1-shell, 2-movable plate, 3-observation window, 4-control panel, 5-reaction chamber, 6-heating plate, 7-pot body, 8-fixed plate, 9-control button and 10-heat dissipation hole.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: sn (tin)3O4-TiO2The heterojunction magnetic photocatalytic composite adsorbing material comprises the following formula raw materials in parts by weight: 14-26 parts of magnetic chitosan-graphene and 50-58 parts of Ce-doped porous Sn3O424-28 parts of TiCl4。
The preparation method of the magnetic chitosan-graphene comprises the following steps:
(1) adding absolute ethyl alcohol solvent and Co into a reaction bottle3O4、Fe2O3ZnO and La2O3The weight molar ratio of the four substances is 0.6:0.4:0.01-0.1:1.9-1.99, the solution is transferred into a star ball mill, the revolution speed is 600 plus material rotation speed is 620rpm, the rotation speed is 120 plus material rotation speed is 150rpm, ball milling is carried out for 6-10h until the materials completely pass through a 600 plus material 800 mesh screen, the mixed product is placed into a vacuum hot-pressing sintering furnace, the sintering pressure is 25-30MPa, the heating rate is 5-10 ℃/min, the heat preservation and the calcination are carried out for 2-3h at 880 plus material temperature of 900 ℃, the temperature is raised to 1100 plus material temperature of 1130 ℃, the heat preservation and the calcination are carried out for 4-6h, the sintered product is lanthanum-doped zinc-cobalt ferrite, the chemical expression is Zn-doped zinc-cobalt0.4Co0.6La0.01-0.1Fe1.9-1.99O4。
(2) Adding 4-8% by mass of acetic acid solution into a reaction bottle, adding chitosan, carboxylated graphene and lanthanum-doped zinc-cobalt ferrite, placing the reaction bottle into an ultrasonic treatment instrument, heating to 60-70 ℃, carrying out ultrasonic dispersion treatment for 2-3h, adding a catalyst of p-toluenesulfonic acid into the reaction bottle, wherein the mass ratio of the chitosan, the carboxylated graphene, the lanthanum-doped zinc-cobalt ferrite to the p-toluenesulfonic acid is 5-6:1:4.5-5:0.005-0.008, transferring the solution into a hydrothermal synthesis reaction kettle, placing the hydrothermal synthesis reaction kettle into a reaction kettle heating box, heating to 130-10 ℃, reacting for 6-8h, cooling the solution, adding NaOH to adjust the pH of the solution to 9-10, adding glyoxal solution, continuing heating to 100-120 ℃ in the reaction kettle heating box, reacting for 4-6h, and cooling the solution to room temperature, distilling the solution under reduced pressure to remove the solvent, washing the solid product with a proper amount of distilled water, fully drying, and passing the solid product through a ball mill until the material passes through a 800-mesh screen with 1000 meshes to prepare the obtained magnetic chitosan-graphene.
Ce doped porous Sn3O4The preparation method comprises the following steps:
(1) adding NaOH solution with pH of 12-13 into a reaction bottle, and then adding SnCl2、CeCl3And sodium citrate with the molar ratio of 30-40:12-15:1, placing a reaction bottle in an ultrasonic treatment instrument, heating to 70-80 ℃, performing ultrasonic dispersion treatment for 1-2h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the solution in a reaction kettle heating box, heating to 160-170 ℃, reacting for 15-20h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ce-doped porous Sn3O4。
Sn3O4-TiO2The preparation method of the heterojunction magnetic photocatalytic composite adsorbing material comprises the following steps:
(1) adding ethanol and propylene glycol solvent into a reaction bottle, wherein the volume ratio of the ethanol to the propylene glycol solvent is 1.5-2:1, and then adding 14-26 parts of magnetic chitosan-graphene and 50-58 parts of Ce-doped porous Sn3O4And 24-28 parts of TiCl4Heating the solution in a constant temperature water bath kettle to 50-60 deg.C, and constant temperature water bathThe pot comprises a shell, a movable plate is fixedly mounted at the upper end of the shell, an observation window is formed in the side face of the shell, a control panel is fixedly mounted at the upper end of the left side of the movable plate, a reaction chamber is fixedly mounted on the upper surface of the movable plate, heating plates are fixedly mounted in the inner part of the reaction chamber, a pot body is movably mounted on the heating plates, a fixing plate is fixedly mounted on the upper surface of the movable plate and located between the two heating plates, a control button is movably mounted on the upper surface of the movable plate, heat dissipation holes are fixedly mounted in the inner part of the shell, the inner part of the shell is uniformly stirred and reacts for 15-20 hours, an acetone solvent is added into the solution and stirred for3O4-TiO2A heterojunction magnetic photocatalytic composite adsorption material.
Example 1
(1) Preparing a lanthanum-doped zinc-cobalt ferrite component 1: adding absolute ethyl alcohol solvent and Co into a reaction bottle3O4、Fe2O3ZnO and La2O3The weight molar ratio of the four substances is 0.6:0.4:0.01:1.99, the solution is transferred into a ball mill, the revolution speed is 600rpm, the rotation speed is 120rpm, the ball milling is carried out for 6h until all the materials pass through a 600-mesh screen, the mixed product is placed into a vacuum hot-pressing sintering furnace, the sintering pressure is 25MPa, the heating rate is 5 ℃/min, the heat preservation and the calcination are carried out for 2h at 880 ℃, the temperature is raised to 1100 ℃, the heat preservation and the sintering are carried out for 4h, the sintered product is a lanthanum-doped zinc-cobalt ferrite component 1, the chemical expression is Zn0.4Co0.6La0.01Fe1.99O4。
(2) Preparing a magnetic chitosan-graphene component 1: adding 4 mass percent acetic acid solution into a reaction bottle, adding 1 component of chitosan, carboxylated graphene and lanthanum-doped zinc-cobalt ferrite, placing the reaction bottle into an ultrasonic treatment instrument, heating to 60 ℃, carrying out ultrasonic dispersion treatment for 2 hours, adding a catalyst of p-toluenesulfonic acid into the reaction bottle, wherein the mass ratio of chitosan, carboxylated graphene, lanthanum-doped zinc-cobalt ferrite to p-toluenesulfonic acid is 5:1:4.5:0.005, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 130 ℃, reacting for 6 hours, cooling the solution, adding NaOH to adjust the pH of the solution to 9, adding glyoxal solution, continuing heating to 100 ℃ in the reaction kettle heating box, reacting for 4 hours, cooling the solution to room temperature, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with a proper amount of distilled water, fully drying, passing the solid product through a ball mill until the material passes through a 800-mesh screen, the magnetic chitosan-graphene component 1 is prepared.
(3) Preparing to obtain Ce doped porous Sn3O4Component 1: adding NaOH solution with pH value of 12 into a reaction bottle, and then adding SnCl2、CeCl3And sodium citrate with the molar ratio of 30:12:1, placing a reaction bottle in an ultrasonic treatment instrument, heating to 70 ℃, performing ultrasonic dispersion treatment for 1h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 160 ℃, reacting for 15h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ce-doped porous Sn3O4And (3) component 1.
(4) Preparation of Sn3O4-TiO2Heterojunction magnetic photocatalytic composite adsorbing material 1: adding ethanol and propylene glycol solvent into a reaction bottle, wherein the volume ratio of the ethanol to the propylene glycol solvent is 1.5:1, and then adding 26 parts of magnetic chitosan-graphene component 1 and 50 parts of Ce-doped porous Sn3O4Components 1 and 24 parts of TiCl4The solution is placed in a constant-temperature water bath kettle and heated to 50 ℃, the constant-temperature water bath kettle comprises a shell, a movable plate is fixedly mounted at the upper end of the shell, an observation window is formed in the side face of the shell, a control panel is fixedly mounted at the upper end of the left side of the movable plate, a reaction cavity is fixedly mounted on the upper surface of the movable plate, a heating plate is fixedly mounted inside the reaction cavity, a pot body is movably mounted on the heating plate, a fixed plate is fixedly mounted on the upper surface of the movable plate and located between the two heating plates, a control button is movably mounted on the upper surface of the movable plate, heat dissipation holes are fixedly mounted inside the shell, the solution is stirred at a constant speed for 15 hours to react, an acetone solvent is added into the solution, the solution3O4-TiO2A heterojunction magnetic photocatalytic composite adsorption material 1.
Example 2
(1) Preparing a lanthanum-doped zinc-cobalt ferrite component 2: adding absolute ethyl alcohol solvent and Co into a reaction bottle3O4、Fe2O3ZnO and La2O3The weight molar ratio of the four substances is 0.6:0.4:0.03:1.97, the solution is transferred into a star ball mill, the revolution speed is 620rpm, the rotation speed is 150rpm, ball milling is carried out for 10 hours until all the materials pass through a 600-mesh screen, the mixed product is placed into a vacuum hot-pressing sintering furnace, the sintering pressure is 25MPa, the heating rate is 10 ℃/min, heat preservation and calcination are carried out for 2 hours at 900 ℃, the temperature is raised to 1130 ℃, heat preservation and sintering are carried out for 4 hours, the sintered product is a lanthanum-doped zinc-cobalt ferrite component 2, the chemical expression is Zn0.4Co0.6La0.03Fe1.97O4。
(2) Preparing a magnetic chitosan-graphene component 2: adding 8 mass percent acetic acid solution into a reaction bottle, adding 2 components of chitosan, carboxylated graphene and lanthanum-doped zinc-cobalt ferrite, placing the reaction bottle into an ultrasonic treatment instrument, heating to 60 ℃, carrying out ultrasonic dispersion treatment for 2 hours, adding a catalyst of p-toluenesulfonic acid into the reaction bottle, wherein the mass ratio of chitosan, carboxylated graphene, lanthanum-doped zinc-cobalt ferrite to p-toluenesulfonic acid is 6:1:4.5:0.005, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 130 ℃, reacting for 8 hours, cooling the solution, adding NaOH to adjust the pH of the solution to 9, adding glyoxal solution, continuing heating to 100 ℃ in the reaction kettle heating box, reacting for 6 hours, cooling the solution to room temperature, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with a proper amount of distilled water, fully drying, passing the solid product through a ball mill until the material passes through a 1000-mesh screen, preparing the obtained magnetic chitosan-graphene component 2.
(3) Preparing to obtain Ce doped porous Sn3O4And (2) component: adding NaOH solution with pH value of 12 into a reaction bottle, and then adding SnCl2、CeCl3And sodium citrate with the molar ratio of 40:12:1, placing the reaction bottle in an ultrasonic treatment instrument, heating to 70 ℃,performing ultrasonic dispersion treatment for 1h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 170 ℃, reacting for 15h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ce-doped porous Sn3O4And (3) component 2.
(4) Preparation of Sn3O4-TiO2Heterojunction magnetic photocatalytic composite adsorbing material 2: adding ethanol and propylene glycol solvent into a reaction bottle, wherein the volume ratio of the ethanol to the propylene glycol solvent is 2:1, and then adding 23 parts of magnetic chitosan-graphene component 2 and 52 parts of Ce-doped porous Sn3O4Component 2 and 25 parts of TiCl4The solution is placed in a constant-temperature water bath kettle and heated to 50 ℃, the constant-temperature water bath kettle comprises a shell, a movable plate is fixedly mounted at the upper end of the shell, an observation window is formed in the side face of the shell, a control panel is fixedly mounted at the upper end of the left side of the movable plate, a reaction cavity is fixedly mounted on the upper surface of the movable plate, a heating plate is fixedly mounted inside the reaction cavity, a pot body is movably mounted on the heating plate, a fixed plate is fixedly mounted on the upper surface of the movable plate and located between the two heating plates, a control button is movably mounted on the upper surface of the movable plate, heat dissipation holes are fixedly mounted inside the shell, the solution is stirred at a constant speed for 20 hours, an acetone solvent is added into the solution, the solution is stirred3O4-TiO2And a heterojunction magnetic photocatalytic composite adsorbing material 2.
Example 3
(1) Preparing a lanthanum-doped zinc-cobalt ferrite component 3: adding absolute ethyl alcohol solvent and Co into a reaction bottle3O4、Fe2O3ZnO and La2O3The weight molar ratio of the four substances is 0.6:0.4:0.05:1.95, the solution is transferred into a star ball mill, the revolution speed is 610rpm, the rotation speed is 130rpm, the ball milling is carried out for 8 hours until all the materials pass through a 800-mesh screen, the mixed product is placed into a vacuum hot-pressing sintering furnace, the sintering pressure is 28MPa, the heating rate is 8 ℃/min, the heat preservation and the calcination are carried out for 2.5 hours at 890 ℃, the temperature is raised to 1120 ℃, the heat preservation and the sintering are carried out for 5 hours, and the sintering product is obtainedThe material is a lanthanum-doped zinc-cobalt ferrite component 3, and the chemical expression is Zn0.4Co0.6La0.05Fe1.95O4。
(2) Preparing a magnetic chitosan-graphene component 3: adding an acetic acid solution with the mass fraction of 6% into a reaction bottle, adding a chitosan, carboxylated graphene and lanthanum-doped zinc-cobalt ferrite component 3, placing the reaction bottle into an ultrasonic treatment instrument, heating to 65 ℃, carrying out ultrasonic dispersion treatment for 2.5h, adding a catalyst of p-toluenesulfonic acid into the reaction bottle, wherein the mass ratio of the chitosan, carboxylated graphene, lanthanum-doped zinc-cobalt ferrite and p-toluenesulfonic acid is 5.5:1:4.8:0.007, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle into a reaction kettle heating box, heating to 140 ℃, reacting for 7h, cooling the solution, adding NaOH to adjust the pH of the solution to 10, adding an glyoxal solution, continuing heating to 110 ℃ in the reaction kettle heating box, reacting for 5h, cooling the solution to room temperature, distilling the solution under reduced pressure to remove the solvent, washing the solid product with a proper amount of distilled water, fully drying, passing the solid product through a ball mill until the material passes through a screen of 1000 meshes, preparing the obtained magnetic chitosan-graphene component 3.
(3) Preparing to obtain Ce doped porous Sn3O4And (3) component: adding NaOH solution with pH value of 13 into a reaction bottle, and then adding SnCl2、CeCl3And sodium citrate with the molar ratio of 35:13:1, placing a reaction bottle in an ultrasonic treatment instrument, heating to 75 ℃, performing ultrasonic dispersion treatment for 1.5h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a reaction kettle heating box, heating to 165 ℃, reacting for 18h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ce-doped porous Sn3O4And (3) component.
(4) Preparation of Sn3O4-TiO2Heterojunction magnetic photocatalytic composite adsorbing material 3: adding ethanol and propylene glycol solvent into a reaction bottle, wherein the volume ratio of the ethanol to the propylene glycol solvent is 1.7:1, and then adding 20 parts of magnetic chitosan-graphene component 3 and 54 parts of Ce-doped porous Sn3O4Components 3 and 26 parts of TiCl4Placing the solution in a constantHeating to 55 ℃ in the warm water bath, the constant temperature water bath includes the casing, and the upper end fixed mounting of casing has the fly leaf, and the observation window has been seted up to the side of casing, and the left upper end fixed mounting of fly leaf has control panel, and the last fixed surface of fly leaf installs the reaction chamber, and the inside fixed mounting of reaction chamber has the hot plate, and the movable mounting of hot plate has the pot body, and the upper surface of fly leaf just is located fixed mounting between two hot plates has a fixed plate, and the last fixed surface movable mounting of fly leaf has control button, the inside fixed mounting of casing has the louvre, at the uniform velocity stirring reaction 17h, adds the acetone solvent to the solution, stirs 8h, with the concentrated solvent of detaching of solution decompression, uses the3O4-TiO2And a heterojunction magnetic photocatalytic composite adsorbing material 3.
Example 4
(1) Preparing a lanthanum-doped zinc-cobalt ferrite component 4: adding absolute ethyl alcohol solvent and Co into a reaction bottle3O4、Fe2O3ZnO and La2O3The weight molar ratio of the four substances is 0.6:0.4:0.07:1.93, the solution is transferred into a ball mill, the revolution speed is 600rpm, the rotation speed is 150rpm, the ball milling is carried out for 10h until all the materials pass through a 800-mesh screen, the mixed product is placed into a vacuum hot-pressing sintering furnace, the sintering pressure is 30MPa, the heating rate is 10 ℃/min, the heat preservation and the calcination are carried out for 3h at 880 ℃, the temperature is raised to 1100 ℃, the heat preservation and the sintering are carried out for 4h, the sintered product is a lanthanum-doped zinc-cobalt ferrite component 4, the chemical expression is Zn0.4Co0.6La0.07Fe1.93O4。
(2) Preparing a magnetic chitosan-graphene component 4: adding 8 mass percent acetic acid solution into a reaction bottle, adding 4 components of chitosan, carboxylated graphene and lanthanum-doped zinc-cobalt ferrite, placing the reaction bottle into an ultrasonic treatment instrument, heating to 70 ℃, carrying out ultrasonic dispersion treatment for 3 hours, adding a catalyst of p-toluenesulfonic acid into the reaction bottle, wherein the mass ratio of chitosan, carboxylated graphene, lanthanum-doped zinc-cobalt ferrite to p-toluenesulfonic acid is 5:1:5:0.006, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle into a reaction kettle heating box, heating to 150 ℃, reacting for 6 hours, cooling the solution, adding NaOH to adjust the pH of the solution to 10, adding glyoxal solution, continuing heating to 120 ℃ in the reaction kettle heating box, reacting for 4 hours, cooling the solution to room temperature, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with an appropriate amount of distilled water, fully drying, passing the solid product through a ball mill until the material passes through an 800-mesh screen, the magnetic chitosan-graphene component 4 is prepared.
(3) Preparing to obtain Ce doped porous Sn3O4And (4) component: adding NaOH solution with pH value of 13 into a reaction bottle, and then adding SnCl2、CeCl3And sodium citrate with the molar ratio of 40:12:1, placing a reaction bottle in an ultrasonic treatment instrument, heating to 70 ℃, performing ultrasonic dispersion treatment for 1h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 170 ℃, reacting for 15h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ce-doped porous Sn3O4And (4) component.
(4) Preparation of Sn3O4-TiO2Heterojunction magnetic photocatalytic composite adsorbing material 4: adding ethanol and propylene glycol solvent into a reaction bottle, wherein the volume ratio of the ethanol to the propylene glycol solvent is 2:1, and then adding 17 parts of magnetic chitosan-graphene component 4 and 56 parts of Ce-doped porous Sn3O4Components 4 and 27 parts of TiCl4The solution is placed in a constant-temperature water bath kettle and heated to 60 ℃, the constant-temperature water bath kettle comprises a shell, a movable plate is fixedly mounted at the upper end of the shell, an observation window is formed in the side face of the shell, a control panel is fixedly mounted at the upper end of the left side of the movable plate, a reaction cavity is fixedly mounted on the upper surface of the movable plate, a heating plate is fixedly mounted inside the reaction cavity, a pot body is movably mounted on the heating plate, a fixed plate is fixedly mounted on the upper surface of the movable plate and located between the two heating plates, a control button is movably mounted on the upper surface of the movable plate, heat dissipation holes are fixedly mounted inside the shell, the solution is stirred at a constant speed for 15 hours to react for 15 hours, an acetone solvent is added into the solution3O4-TiO2And a heterojunction magnetic photocatalytic composite adsorbing material 4.
Example 5
(1) Preparing a lanthanum-doped zinc-cobalt ferrite component 5: adding absolute ethyl alcohol solvent and Co into a reaction bottle3O4、Fe2O3ZnO and La2O3The weight molar ratio of the four substances is 0.6:0.4:0.1:1.9, the solution is transferred into a star ball mill, the revolution speed is 620rpm, the rotation speed is 150rpm, the ball milling is carried out for 10 hours until all the materials pass through a 800-mesh screen, the mixed product is placed into a vacuum hot-pressing sintering furnace, the sintering pressure is 30MPa, the heating rate is 10 ℃/min, the heat preservation and the calcination are carried out for 3 hours at 900 ℃, the temperature is raised to 1130 ℃, the heat preservation and the sintering are carried out for 4 hours, the sintered product is a lanthanum-doped zinc-cobalt ferrite component 5, the chemical expression is Zn0.4Co0.6La0.1Fe1.9O4。
(2) Preparing a magnetic chitosan-graphene component 5: adding 8 mass percent acetic acid solution into a reaction bottle, adding 5 components of chitosan, carboxylated graphene and lanthanum-doped zinc-cobalt ferrite, placing the reaction bottle into an ultrasonic treatment instrument, heating to 70 ℃, carrying out ultrasonic dispersion treatment for 3 hours, adding a catalyst of p-toluenesulfonic acid into the reaction bottle, wherein the mass ratio of chitosan, carboxylated graphene, lanthanum-doped zinc-cobalt ferrite to p-toluenesulfonic acid is 6:1:5:0.008, transferring the solution into a hydrothermal synthesis reaction kettle, placing the reaction kettle into a reaction kettle heating box, heating to 150 ℃, reacting for 8 hours, cooling the solution, adding NaOH to adjust the pH of the solution to 10, adding glyoxal solution, continuing heating to 120 ℃ in the reaction kettle heating box, reacting for 6 hours, cooling the solution to room temperature, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with a proper amount of distilled water, fully drying, passing the solid product through a ball mill until the material passes through a 1000-mesh screen, preparing the obtained magnetic chitosan-graphene component 5.
(3) Preparing to obtain Ce doped porous Sn3O4And (5) component: adding NaOH solution with pH value of 13 into a reaction bottle, and then adding SnCl2、CeCl3And sodium citrate with the molar ratio of 40:15:1, placing the reaction bottle in a super-high reaction kettleHeating to 80 ℃ in a sound treatment instrument, carrying out ultrasonic dispersion treatment for 2h, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in a heating box of the reaction kettle, heating to 170 ℃, reacting for 20h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with a proper amount of distilled water, and fully drying to prepare the Ce-doped porous Sn3O4And (5) component.
(4) Preparation of Sn3O4-TiO2Heterojunction magnetic photocatalytic composite adsorbent 5: adding ethanol and propylene glycol solvent into a reaction bottle, wherein the volume ratio of the ethanol to the propylene glycol solvent is 2:1, and then adding 14 parts of magnetic chitosan-graphene component 5 and 58 parts of Ce-doped porous Sn3O4Components 5 and 28 parts of TiCl4The solution is placed in a constant-temperature water bath kettle and heated to 60 ℃, the constant-temperature water bath kettle comprises a shell, a movable plate is fixedly mounted at the upper end of the shell, an observation window is formed in the side face of the shell, a control panel is fixedly mounted at the upper end of the left side of the movable plate, a reaction cavity is fixedly mounted on the upper surface of the movable plate, a heating plate is fixedly mounted inside the reaction cavity, a pot body is movably mounted on the heating plate, a fixed plate is fixedly mounted on the upper surface of the movable plate and located between the two heating plates, a control button is movably mounted on the upper surface of the movable plate, heat dissipation holes are fixedly mounted inside the shell, the solution is stirred at a constant speed for 20 hours, an acetone solvent is added into the solution, the solution is stirred3O4-TiO2And a heterojunction magnetic photocatalytic composite adsorbing material 5.
To the reaction flask was added a 5% aqueous methylene blue solution, each containing 2% of Sn as in examples 1 to 53O4-TiO2A200W xenon lamp is used as a light source, the illumination is carried out for 24h, an SP-2500 ultraviolet visible spectrophotometer is used for detecting the residual concentration of methylene blue, the degradation rate of the methylene blue is calculated, the degradation rate is (0.05-residual concentration of methylene blue)/0.05, and the test standard is GB/T23762 one-year 2009.
Examples 1-5 degradation rates for methylene blue
In summary, the one Sn3O4-TiO2Hetero-junction magnetic photocatalytic composite adsorption material, Ce doped Sn3O4Partial Sn atom lattice is replaced, the forbidden bandwidth is reduced, and the distance between the valence band and the conduction band is shortened, so that the Sn is widened3O4Can absorb light in a wave band, enhances the utilization rate of the photocatalytic material to light energy, and enables Sn to be doped by Ce3O4A large number of oxygen defects are generated in Sn3O4Oxygen defect state generated at the bottom of the conduction band, photo-generated electrons in the valence band are excited to oxygen vacancy energy level and then jump to the conduction band, and holes are left in the valence band, so that the oxygen defect on the conduction band can capture the photo-generated electrons, the recombination rate of the photo-generated electrons and the holes is reduced, the photocatalytic activity of the material is enhanced, the atomic radius of Ce is larger, and the Ce is doped in Sn3O4A large amount of mesoporous structures are formed on the surface of the lead-free tin alloy, and Sn is increased3O4The specific surface area and the light radiation area, thereby enhancing the light responsiveness and the light energy absorption rate of the photocatalytic material.
Sn prepared by in situ method3O4-TiO2Heterojunction, TiO2Has a very wide ultraviolet-visible light absorption band, improves the light absorption efficiency of the heterojunction, and when light is radiated onto the heterojunction, Sn is formed3O4The generated photo-generated electrons are from Sn3O4To TiO2On the conduction band of TiO2Generated holes migrate from Sn to Sn3O4In valence band, the migration and transmission of the photoproduction electrons and the holes are promoted, the separation efficiency of the heterojunction photoproduction electrons and the holes is improved, and the recombination of the photoproduction electrons and the holes is effectively inhibited, so that the performance of photocatalytic degradation of organic pollutants is enhanced.
Sn loaded by using magnetic chitosan-graphene material with huge specific surface area3O4-TiO2The heterojunction forms a composite material, and Sn is avoided3O4-TiO2Heterojunction in waterThe zinc-cobalt ferrite in the magnetic chitosan-graphene is doped with lanthanum to form a cubic spinel structure, so that the lattice parameter and the crystallization rate of the crystal are increased, the magnetic permeability of the cobalt ferrite is reduced, the lanthanum-doped zinc-cobalt ferrite shows excellent magnetism, and the magnetic chitosan-graphene can be used for treating Cu in sewage2+、Cd2+The heavy metal ions are magnetically adsorbed, and a large amount of hydroxyl and amino in the chitosan can be complexed with the metal ions, so that the adsorption effect of the photocatalytic composite adsorption material on the heavy metals and the ions thereof is enhanced, the catalytic composite adsorption material has good magnetism, the composite adsorption material can be recovered through an external magnetic field, the use efficiency is improved, and the secondary pollution is avoided.
Claims (8)
1. Sn (tin)3O4-TiO2The heterojunction magnetic photocatalytic composite adsorbing material comprises the following formula raw materials in parts by weight, and is characterized in that: 14-26 parts of magnetic chitosan-graphene and 50-58 parts of Ce-doped porous Sn3O424-28 parts of TiCl4。
2. Sn according to claim 13O4-TiO2Heterojunction magnetism photocatalysis composite adsorption material, its characterized in that: the preparation method of the magnetic chitosan-graphene comprises the following steps:
(1) adding Co into absolute ethyl alcohol solvent3O4、Fe2O3ZnO and La2O3Transferring the solution into a star ball mill, performing ball milling for 6-10h at the revolution speed of 600-plus-620 rpm and the rotation speed of 120-plus-150 rpm until the materials completely pass through a 600-plus-800-mesh screen, placing the mixed product in a vacuum hot-pressing sintering furnace, performing heat preservation and calcination for 2-3h at the temperature of 880-plus-900 ℃ at the temperature of 5-10 ℃/min, and then heating to 1100-plus-1130 ℃ for 4-6h, wherein the sintered product is lanthanum-doped zinc-cobalt ferrite.
(2) Adding chitosan, carboxylated graphene and lanthanum-doped zinc-cobalt ferrite into an acetic acid solution with the mass fraction of 4-8%, performing ultrasonic dispersion treatment on the solution at 60-70 ℃ for 2-3h, adding a catalyst p-toluenesulfonic acid into the solution, transferring the solution into a reaction kettle, heating to 130-150 ℃, reacting for 6-8h, cooling the solution, adding NaOH to adjust the pH of the solution to 9-10, adding a glyoxal solution, continuing heating to 100-120 ℃ in a reaction kettle heating box, reacting for 4-6h, removing the solvent from the solution, washing a solid product, drying, and passing the solid product through a ball mill until the material passes through a 800-mesh 1000-mesh screen to prepare the magnetic chitosan-graphene.
3. Sn according to claim 23O4-TiO2Heterojunction magnetism photocatalysis composite adsorption material, its characterized in that: the Co3O4、Fe2O3ZnO and La2O3The molar ratio of the substances is 0.6:0.4:0.01-0.1:1.9-1.99, and the chemical expression of the lanthanum-doped zinc-cobalt ferrite is Zn0.4Co0.6La0.01-0.1Fe1.9-1.99O4。
4. Sn according to claim 23O4-TiO2Heterojunction magnetism photocatalysis composite adsorption material, its characterized in that: the mass ratio of the chitosan, the carboxylated graphene, the lanthanum-doped zinc-cobalt ferrite and the p-toluenesulfonic acid is 5-6:1:4.5-5: 0.005-0.008.
5. Sn according to claim 13O4-TiO2Heterojunction magnetism photocatalysis composite adsorption material, its characterized in that: the Ce doped porous Sn3O4The preparation method comprises the following steps:
(1) adding SnCl into NaOH solution with pH value of 12-132、CeCl3And sodium citrate, performing ultrasonic dispersion treatment on the solution at 70-80 ℃ for 1-2h, transferring the solution into a reaction kettle, heating to 160-170 ℃, reacting for 15-20h, filtering the solution to remove the solvent, washing a solid product, drying, and preparing the productObtaining Ce doped porous Sn3O4。
6. Sn according to claim 53O4-TiO2Heterojunction magnetism photocatalysis composite adsorption material, its characterized in that: the SnCl2、CeCl3The molar ratio of the sodium citrate to the sodium citrate is 30-40:12-15: 1.
7. Sn according to claim 13O4-TiO2Heterojunction magnetism photocatalysis composite adsorption material, its characterized in that: the Sn3O4-TiO2The preparation method of the heterojunction magnetic photocatalytic composite adsorbing material comprises the following steps:
(1) adding 14-26 parts of magnetic chitosan-graphene and 50-58 parts of Ce-doped porous Sn into ethanol and propylene glycol solvent with the volume ratio of 1.5-2:13O4And 24-28 parts of TiCl4Heating the solution in a constant temperature water bath to 50-60 deg.C, reacting for 15-20h, adding acetone solvent into the solution, stirring for 6-10h, removing solvent from the solution, washing the solid product, drying, and preparing to obtain Sn3O4-TiO2A heterojunction magnetic photocatalytic composite adsorption material.
8. Sn according to claim 73O4-TiO2Heterojunction magnetism photocatalysis composite adsorption material, its characterized in that: constant temperature water-bath includes casing (1), the upper end fixed mounting of casing (1) has fly leaf (2), observation window (3) have been seted up to the side of casing (1), the left upper end fixed mounting of fly leaf (2) has control panel (4), the last fixed surface of fly leaf (2) installs reaction chamber (5), the inside fixed mounting of reaction chamber (5) has hot plate (6), the movable mounting of hot plate (6) has the pot body (7), the upper surface of fly leaf (2) just is located fixed mounting between two hot plate (6) has fixed plate (8), the last fixed surface movable mounting of fly leaf (2) has control button (9), the inside fixed mounting of (1) has louvre (10).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010462743.6A CN111558364A (en) | 2020-05-27 | 2020-05-27 | Sn (tin)3O4-TiO2Heterojunction magnetic photocatalytic composite adsorption material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010462743.6A CN111558364A (en) | 2020-05-27 | 2020-05-27 | Sn (tin)3O4-TiO2Heterojunction magnetic photocatalytic composite adsorption material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111558364A true CN111558364A (en) | 2020-08-21 |
Family
ID=72073676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010462743.6A Withdrawn CN111558364A (en) | 2020-05-27 | 2020-05-27 | Sn (tin)3O4-TiO2Heterojunction magnetic photocatalytic composite adsorption material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111558364A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116603514A (en) * | 2023-07-18 | 2023-08-18 | 湖南亿康环保科技有限公司 | Sewage treatment agent for treating groundwater pollution and preparation method thereof |
-
2020
- 2020-05-27 CN CN202010462743.6A patent/CN111558364A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116603514A (en) * | 2023-07-18 | 2023-08-18 | 湖南亿康环保科技有限公司 | Sewage treatment agent for treating groundwater pollution and preparation method thereof |
| CN116603514B (en) * | 2023-07-18 | 2023-11-14 | 湖南亿康环保科技有限公司 | Sewage treatment agent for treating groundwater pollution and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106732524B (en) | Alpha/beta-bismuth oxide phase heterojunction photocatalyst and preparation method and application thereof | |
| CN111437867B (en) | Composite photocatalyst containing tungsten oxide and preparation method and application thereof | |
| CN107899592B (en) | Magnetic recyclable flaky NiFe2O4Preparation method and application of/BiOI composite nano material | |
| CN109317137B (en) | Hydrotalcite and bismuth molybdate heterojunction composite photocatalyst and preparation method and application thereof | |
| CN106334554A (en) | ZnO/Ag composite nano-photocatalyst with high-efficiency photocatalytic activity under visible lights | |
| CN102151577A (en) | Ag3PO4/Mg-Al LDO (Layered Double Oxide) visible light composite photo catalyst, preparation and application thereof | |
| CN111453804A (en) | Preparation method of iron-doped graphite-like phase carbon nitride/graphene multifunctional nano composite material | |
| CN105498820A (en) | Preparing method for high visible-light electron transfer Au/g-C3N4 supported photocatalytic material | |
| CN104549281A (en) | Active graphene-metal oxide composite photocatalyst and preparation method and application thereof | |
| CN107935103A (en) | A kind for the treatment of process of silver-based composite photocatalyst for degrading dyeing waste water | |
| CN105536843A (en) | Preparation method of highly visible light electron transfer g-C3N4/ Au/TiO2 Z type photocatalyst | |
| CN111558364A (en) | Sn (tin)3O4-TiO2Heterojunction magnetic photocatalytic composite adsorption material and preparation method thereof | |
| Jiang et al. | Controllable growth of MoS 2 nanosheets on TiO 2 burst nanotubes and their photocatalytic activity | |
| Sharafinia et al. | Decoration of ZnFe2O4 and UiO-66 over g-C3N4 as magnetically novel reusable visible light photocatalyst for degradation of Rh–B | |
| CN112495400B (en) | SnS with S vacancy2Preparation of nanosheet and application thereof in photodegradation of Cr (VI) | |
| Li et al. | Nano-flower like NiO modified BiOBr composites with direct Z-scheme: Improved visible light degradation activity for dyes | |
| CN107899594B (en) | Carbon-point-modified copper hydroxyphosphate photocatalytic material and preparation method thereof | |
| CN104138762A (en) | Preparation method and application of cubic-structure CuCr2O4 visible light photocatalyst | |
| CN111592029A (en) | Preparation method of rod-shaped silver-plated cerium dioxide | |
| CN108187701B (en) | Preparation method of AgCl/BiOCl photocatalyst with tubular AgCl structure | |
| CN108940348B (en) | Silver chromate/sulfur-doped nitrogen carbon Z-type photocatalyst and preparation method thereof | |
| CN108940326B (en) | Preparation method of visible light response zinc stannate/carbon/silver bromide nano composite photocatalyst | |
| CN108298632B (en) | Nano TiO (titanium dioxide)2Process for degrading dye wastewater by using photocatalyst | |
| CN115779889A (en) | Lignin carbon/bismuth molybdate composite photocatalyst and preparation method and application thereof | |
| Xu et al. | Interfacial synergy of Ag nanoparticles and ultrathin Bi2WO6 nanosheets for boosting organic pollutants photodegradation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200821 |