CN110013882B - Preparation method of high-performance recyclable photocatalytic magnetic nano material - Google Patents
Preparation method of high-performance recyclable photocatalytic magnetic nano material Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 94
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011246 composite particle Substances 0.000 claims abstract description 50
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 46
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 43
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 43
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 43
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 43
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000006185 dispersion Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000001509 sodium citrate Substances 0.000 claims description 9
- 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 9
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 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 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 10
- 239000004408 titanium dioxide Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000002122 magnetic nanoparticle Substances 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract 3
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 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 15
- 229960000907 methylthioninium chloride Drugs 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000004032 porphyrins Chemical class 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002052 molecular layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000007281 self degradation Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- -1 titanic acidTetrabutyl ester Chemical class 0.000 description 2
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003637 steroidlike Effects 0.000 description 1
- 238000006467 substitution reaction 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
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- 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
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a high-performance recyclable photocatalytic magnetic nano material, and Fe prepared by a coprecipitation method3O4Magnetic nano particles are used as the core of the composite particles, and SiO is prepared by a sol-gel method2Coated in TiO2With Fe3O4The cores are prevented from being in direct contact with each other to cause the recombination of photogenerated electron hole pairs in the particles, and then a layer of TiO is coated on the photogenerated electron hole pairs by a sol-gel method2Finally, by addition of Fe3O4/SiO2/TiO2The surface is loaded with-NH with positive charge by reacting 3-aminopropyltrimethoxysilane by sol-gel method2And loading the AgNPs and ZnTPPS with negative charges. Fe3O4/SiO2/TiO2The AgNPs/ZnTPPS composite particles have the photocatalysis performance of titanium dioxide and the magnetic performance, so that the AgNPs/ZnTPPS composite particles can be recycled, and the absorption wavelength range of the composite particles is increased by the synergistic effect of the loaded AgNPs, ZnTPPS and the titanium dioxide layer, so that the photocatalysis performance of the composite particles is improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic nano materials, and particularly relates to a preparation method of a high-performance recyclable photocatalytic magnetic nano material.
Background
The magnetic response nano photocatalytic material is characterized in that a nano photocatalyst is loaded or coated on magnetic nano particles which are nano, so that the magnetic response nano photocatalytic material has the excellent characteristics of the photocatalyst and the magnetic response characteristics of the magnetic particles. The main purpose of doing this is therefore to modify some of the non-recyclable photocatalysts into recyclable magnetic nano-photocatalytic materials. Fe3O4The nano-particles have fast and efficient magnetic response under the action of a magnetic field, and are widely applied in many fields. Their insolubility and superparamagnetism enable the catalyst to be separated from the reaction mixture without failure and with high efficiency. Recently, Fe3O4Nanoparticles are considered to be reliable, readily available, high surface area supports in catalytic conversion. However, Fe as a carrier3O4The nanoparticles are susceptible to air. Therefore, it is necessary to construct a core/shell structure composite carrier, in which Fe is incorporated3O4Nanoclusters serve as a core and functionalized layers serve as a shell. The chemical stability requirement of the shell is high, which is beneficial to the immobilization of the non-steroidal nanoparticles and the catalytic reaction.
In the prior art, chinese patent CN201310120096.0 discloses a magnetic-response nanocomposite particle prepared by using ferroferric oxide as a magnetic carrier core, a silica nano-layer as a protective layer, and modified titanium dioxide as a photocatalyst. However, such composite particles have a technical drawback of low photocatalytic efficiency.
Disclosure of Invention
The invention aims to provide a high-efficiency photocatalytic magnetic nano material which has a compact structure, stable properties, safety, no toxicity and recyclability.
The invention is realized by the following technical scheme.
A preparation method of high-performance recyclable photocatalytic nano-materials comprises the following operation steps:
(1) preparing magnetic nano ferroferric oxide by taking ferric chloride hexahydrate and ferrous sulfate heptahydrate as raw materials by adopting a coprecipitation method, wherein the molar ratio of ferric ions to ferrous ions is 9: 5;
(2) dispersing magnetic nano ferroferric oxide in deionized water, wherein the mass fraction of the magnetic nano ferroferric oxide is 0.8-1.2%, adding tetraethoxysilane with the volume of 1-2% of that of the deionized water and ammonia water with the volume fraction of 20% which is the same as that of the tetraethoxysilane into the deionized water, heating to 55-65 ℃, keeping the temperature at the rotating speed of 180-220r/min for continuous reaction for 7-9 hours, centrifuging, and alternately washing the obtained reaction product with ethanol and deionized water for three times to obtain Fe3O4/SiO2Composite particles;
(3) preparation of Fe3O4/SiO2Heating the anhydrous ethanol dispersion liquid with the composite particle mass fraction of 3-6% to 55-65 ℃ at the rotating speed of 100-120r/min, adding the solution A with the volume of 6-10% of the anhydrous ethanol, continuing stirring for reaction for 7-9h, centrifuging, alternately washing the product with deionized water and ethanol for three times to obtain Fe3O4/SiO2/TiO2The composite particles comprise a liquid A and a liquid B, wherein the liquid A is prepared from the following components in parts by volume: 10-15 parts of tetrabutyl titanate, 7-8 parts of absolute ethyl alcohol, 2-4 parts of 12mol/L hydrochloric acid and 35-45 parts of water;
(4) preparation of Fe3O4/SiO2/TiO23-6% of absolute ethyl alcohol dispersion liquid of composite particles, then adding 3-aminopropyl trimethoxy silane of which the volume is 1-3% of that of the dispersion liquid, uniformly mixing, heating to 80-90 ℃ for reaction for 3-5h, and alternately washing the product with ethyl alcohol and deionized water for three times to obtain Fe3O4/SiO2/TiO2-NH2Composite particles;
(5) preparation of Fe3O4/SiO2/TiO2-NH2An aqueous solution of composite particles with a mass fraction of 3-5%, then adding to it a silver nanodispersion with a volume of 40-50% and a zinc porphyrin with a volume of 0.5-0.9%, which areThe mass fraction of the silver nano in the medium-silver nano dispersion liquid is 0.1 percent, the purity of zinc porphyrin is 98 percent, after reaction is carried out for 1-2 hours at the rotating speed of 120-class/min, the product is washed by deionized water for three times by centrifugation, and then calcination treatment is carried out, thus obtaining the product
Fe3O4/SiO2/TiO2-AgNPs/ZnTPPS。
Specifically, in the step (1), the specific operation of preparing the magnetic nano ferroferric oxide is as follows: dissolving ferric chloride hexahydrate and ferrous sulfate heptahydrate in deionized water, introducing nitrogen for 30min at the rotating speed of 100r/min to remove oxygen in the solution, heating the mixed solution to 30 ℃, adding ammonia water into the mixed solution, adjusting the pH of the mixed solution to 10, continuing introducing nitrogen, stirring the mixed solution at the speed of 100r/min to react for 30min, adding sodium citrate accounting for 15% of the mass of the ferric chloride hexahydrate into the mixed solution, heating the mixture to 70 ℃, stirring the mixed solution at the speed of 500r/min to react for 3h, centrifuging, washing the precipitate with ethanol for three times, and then washing with deionized water for three times to obtain the magnetic nano ferroferric oxide.
Specifically, in the step (5), the silver nano-dispersion is prepared by the following method: weighing 0.1558 parts of sodium citrate by weight, dissolving in 3 parts of ultrapure water for later use, and weighing 0.018 part of AgNO3Dissolving the silver nano dispersion in 100 parts of ultrapure water, heating the solution to boiling by using a heating sleeve at the rotating speed of 100r/min, then quickly adding the prepared sodium citrate solution, reacting for 3min, starting to turn yellow, gradually deepening the color of the solution to turn brown yellow, finally turning green, continuing to react for 1h, stopping the reaction, and centrifuging the obtained product by using a centrifugal machine, wherein the supernatant is the silver nano dispersion.
Specifically, in the step (5), the temperature of the calcination treatment is 490-510 ℃, and the time of the calcination treatment is 50-70 min.
According to the technical scheme, the beneficial effects of the invention are as follows:
the high-performance recyclable photocatalytic magnetic nano material prepared by the invention has a core-shell structure and mainly comprises Fe3O4Core, a layer of SiO2The middle protective layer and a layer of TiO loaded with Ag nano particles and Zn porphyrin which are uniformly distributed2A nanolayer. By addition of Fe3O4The nano particles are used as magnetic cores to recycle the photocatalyst; then SiO is used2Coated with Fe3O4Core, effectively protecting the core from Fe3O4The photocatalyst can perform reaction circulation for many times, and the ferroferric oxide is isolated from direct contact with the titanium dioxide, so that Fe is reduced3O4Adverse effects of the core, promoted TiO2Photocatalytic activity of the nanolayer. Is Fe3O4/SiO2The composite particle is coated with 3-aminopropyl trimethoxy silane, and the main purpose is to load positively charged amino groups on the nano composite particle so as to adsorb and load substances which have negative charges and can generate a synergistic effect with titanium dioxide and enhance the photocatalytic performance of the titanium dioxide, Ag nanoparticles (AgNPs) and Zn porphyrin (ZnTPPS) are modified so as to help separate photon-generated electron hole pairs, so that the photocatalytic activity of the composite particle is enhanced, and all coating substances are connected by chemical bonds, are compact in structure and stable in property.
Drawings
FIG. 1 shows the magnetic nano-Fe produced in each stage3O4、Fe3O4/SiO2Composite particles, Fe3O4/SiO2/TiO2Particle size distribution of the composite particles.
FIG. 2 is Fe3O4/SiO2/TiO2Ultraviolet absorption change spectrogram of catalytic degradation of methylene blue by AgNPs/ZnTPPS composite particles.
FIG. 3 is a graph comparing the rate of degraded methylene blue to the rate of self-degradation of methylene blue of the final products of example 1, comparative example 1, and comparative example 2.
FIG. 4 is Fe3O4/SiO2/TiO2-degradation efficiency diagram of AgNPs/ZnTPPS composite particles for methylene blue light catalytic degradation reaction recycling.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
A preparation method of high-performance recyclable photocatalytic nano-materials comprises the following operation steps:
(1) weighing 2.70g FeCl3·6H2O and 1.54gFeSO4·7H2Ultrasonically dissolving O in 200ml of deionized water in a 500ml three-neck flask, introducing nitrogen for 30min at the rotating speed of 100r/min, removing oxygen in the solution, heating to 30 ℃ in a water bath kettle, and slowly adding 4.2ml of NH dropwise under the protection of nitrogen3·H2And O, adjusting the pH value of the solution to 10, when the pH value is adjusted to be about 7, the solution begins to turn black, ferroferric oxide is generated, and stirring is continued for 30min under the protection of N2. Adding 2ml of 0.2g/ml sodium citrate, heating to 70 ℃ in a water bath kettle, reacting for 3 hours under vigorous stirring, washing a product with ethanol for three times, then washing with deionized water for three times to obtain magnetic nano ferroferric oxide, and testing the particle size of the product to obtain the average particle size Xav of the product which is 82.91 nm;
(2) preparing deionized water solution with the mass fraction of 1.0% of magnetic nano ferroferric oxide, measuring 200ml, adding 3ml of ethyl orthosilicate, stirring and dispersing uniformly, slowly adding 3ml of ammonia water, keeping the temperature at the rotating speed of 200r/min for continuous reaction for 8 hours, centrifuging, alternately washing the obtained reaction product with ethanol and deionized water for three times to obtain Fe3O4/SiO2Composite particles;
(3) preparation of Fe3O4/SiO2Taking 100ml of absolute ethyl alcohol dispersion liquid with composite particles of which the mass fraction is 5%, heating to 60 ℃ at the rotating speed of 110r/min, adding 9ml of A liquid, continuing stirring and reacting for 8 hours, centrifuging, and alternately washing a product with deionized water and ethyl alcohol for three times to obtain Fe3O4/SiO2/TiO2The composite particles comprise a liquid A and a liquid B, wherein the liquid A is prepared from the following components: 1.2ml of titanic acidTetrabutyl ester, 7.5ml of absolute ethyl alcohol, 0.3ml of 12mo1/L hydrochloric acid and 4ml of water;
(4) preparation of Fe3O4/SiO2/TiO2Measuring 100ml of absolute ethyl alcohol dispersion liquid with composite particles of which the mass fraction is 5%, adding 2ml of 3-aminopropyl trimethoxy silane, uniformly mixing, heating to 85 ℃, reacting for 4 hours, and alternately washing the product with ethyl alcohol and deionized water for three times to obtain Fe3O4/SiO2/TiO2-NH2Composite particles;
(5) preparation of Fe3O4/SiO2/TiO2-NH2Measuring 30ml of aqueous solution with the composite particles with the mass fraction of 4%, adding 15ml of silver nano dispersion liquid and zinc porphyrin with the volume of 0.25ml of silver nano dispersion liquid, wherein the mass fraction of silver nano in the silver nano dispersion liquid is 0.1%, the purity of the zinc porphyrin is 98%, reacting for 1 hour at the rotating speed of 130r/min, centrifuging, washing the product with deionized water for three times, and calcining at 500 ℃ for 60 minutes to obtain the composite particles
Fe3O4/SiO2/TiO2-AgNPs/ZnTPPS。
Specifically, in the step (5), the silver nano-dispersion is prepared by the following method: 0.1558g of sodium citrate is weighed and dissolved in 3ml of ultrapure water for standby, 0.018g of AgNO is weighed and dissolved3Dissolving in 100ml of ultrapure water, heating by a heating sleeve at the rotating speed of 100r/min until the solution boils, then quickly adding the prepared sodium citrate solution, reacting for 3min, then starting to turn yellow, gradually deepening the color to turn brown yellow, finally turning green, continuing to react for 1h, then stopping the reaction, centrifuging by a centrifuge to obtain the product, and taking the supernatant as the silver nano dispersion liquid.
Comparative example 1
The step (5) is completely the same as the example 1 except that the silver nano dispersion liquid is not added, and Fe is prepared3O4/SiO2/TiO2-ZnTPPS。
Comparative example 2
No zinc porphyrin is added in the step (5), and the rest of the operation steps are completely the same as the example 2, so that Fe is prepared3O4/SiO2/TiO2-AgNPs。
FIG. 1 shows the products of each stage (magnetic nano Fe)3O4、Fe3O4/SiO2Composite particles, Fe3O4/SiO2/TiO2Composite particles), as can be seen from the figure: (1) fe3O4The average particle size of the magnetic nanoparticles is about 82.91nm, the peak is short and wide, the peak top is relatively round, and the data shows that the dispersion index PI is 0.2460, which indicates that the dispersion uniformity is poor; (2) fe3O4/SiO2The average particle diameter of the composite particles is 212.84nm, the peak is short and wide, the peak top is relatively smooth, and the data shows that the dispersion index PI is 0.108, which indicates that the dispersion uniformity is poor, but the dispersion index PI is less than that of Fe3O4The magnetic nano particles are improved probably because the coating of a layer of silicon dioxide reduces the magnetism of the composite particles, delays the agglomeration process of the composite particles and reflects that the silicon dioxide is coated on Fe3O4The surfaces of the magnetic nanoparticles; (3) fe3O4/SiO2/TiO2The average particle diameter of the composite particles was about 234.98nm, the peak was short and broad, and the peak top was relatively gentle, and the data showed that the dispersion index PI was 0.1164, which shows that the dispersion was comparable to Fe3O4/SiO2The composite particles are slightly different, but the titanium dioxide is still successfully coated with Fe in terms of particle size3O4/SiO2The surface of the composite particle. Based on the above data, example 1 has succeeded in forming SiO2And TiO2Coated with Fe3O4On the core.
FIG. 2 is Fe3O4/SiO2/TiO2The ultraviolet absorption change spectrogram of methylene blue catalytically degraded by AgNPs/ZnTPPS composite particles is characterized in that the ultraviolet absorption change spectrogram of the methylene blue at the time of 0min, 10min, 20min, 30min, 40min, 50min and 60min of each curve from top to bottom in sequence, and can be obviously seen from the graph in a xenon lamp and Fe lamp of 300W3O4/SiO2/TiO2Methylene under the catalysis of-AgNPs/ZnTPPS composite particlesThe basic blue is degraded obviously and the degradation rate is faster. From data analysis, the ultraviolet absorption peak value of methylene blue under the photocatalysis of the composite particles is reduced by about 44.22 percent within 60min, which shows that Fe3O4/SiO2/TiO2the-AgNPs/ZnTPPS composite particles have good catalytic degradation effect on methylene blue, and are efficient photocatalysts.
FIG. 3 is a graph comparing the rate of degraded methylene blue to the rate of self-degradation of methylene blue of the final products of example 1, comparative example 1, and comparative example 2. It can be obviously seen from the figure that the composite particles loaded with Ag nanoparticles and the composite particles loaded with Zn porphyrin have certain promotion effects on the degradation of methylene blue, but the effects are too low, about 18.95% and 21.06% of the degradation is respectively carried out within 60min, the catalytic efficiency is not obvious, and the expected requirements are not met; meanwhile, the composite particle loaded with the Ag nano particles and the Zn porphyrin has a quite obvious catalytic degradation effect on methylene blue, and the methylene blue degradation reaches 32.69% within 60 minutes. And the photodegradation rate of the composite particle has no obvious change at the later stage, which shows that the composite particle is relatively stable in the environment and is an excellent photocatalytic nano material.
FIG. 4 is Fe3O4/SiO2/TiO2-degradation efficiency diagram of AgNPs/ZnTPPS composite particles for methylene blue light catalytic degradation reaction recycling. It can be seen from the figure that the efficiency of the prepared composite particles for photocatalytic degradation of methylene blue is still up to more than 80% after 5 times of recycling, which indicates that Fe3O4/SiO2/TiO2the-AgNPs/ZnTPPS composite particles have good stability, the titanium dioxide nano layer is firmly combined with Zn porphyrin and Ag nano particles, and the composite catalyst has longer service life.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art should understand that they can make various changes, modifications, additions and substitutions within the spirit and scope of the present invention.
Claims (4)
1. A preparation method of a high-performance recyclable photocatalytic magnetic nano material is characterized by comprising the following operation steps:
(1) preparing magnetic nano ferroferric oxide by taking ferric chloride hexahydrate and ferrous sulfate heptahydrate as raw materials by adopting a coprecipitation method, wherein the molar ratio of ferric ions to ferrous ions is 9: 5;
(2) dispersing magnetic nano ferroferric oxide in deionized water, wherein the mass fraction of the magnetic nano ferroferric oxide is 0.8-1.2%, adding tetraethoxysilane with the volume of 1-2% of that of the deionized water and ammonia water with the volume fraction of 20% which is the same as that of the tetraethoxysilane into the deionized water, heating to 55-65 ℃, keeping the temperature at the rotating speed of 180-220r/min for continuous reaction for 7-9 hours, centrifuging, and alternately washing the obtained reaction product with ethanol and deionized water for three times to obtain Fe3O4/SiO2Composite particles;
(3) preparation of Fe3O4/SiO2Heating the anhydrous ethanol dispersion liquid with the composite particle mass fraction of 3-6% to 55-65 ℃ at the rotating speed of 100-120r/min, adding the solution A with the volume of 6-10% of the anhydrous ethanol, continuing stirring for reaction for 7-9h, centrifuging, alternately washing the product with deionized water and ethanol for three times to obtain Fe3O4/SiO2/TiO2The composite particles comprise a liquid A and a liquid B, wherein the liquid A is prepared from the following components in parts by volume: 10-15 parts of tetrabutyl titanate, 7-8 parts of absolute ethyl alcohol, 2-4 parts of 12mol/L hydrochloric acid and 35-45 parts of water;
(4) preparation of Fe3O4/SiO2/TiO23-6% of absolute ethyl alcohol dispersion liquid of composite particles, then adding 3-aminopropyl trimethoxy silane of which the volume is 1-3% of that of the dispersion liquid, uniformly mixing, heating to 80-90 ℃ for reaction for 3-5h, and alternately washing the product with ethyl alcohol and deionized water for three times to obtain Fe3O4/SiO2/TiO2-NH2Composite particles;
(5) preparation of Fe3O4/SiO2/TiO2-NH23-5% of composite particle mass fraction aqueous solution,then adding 40-50% of silver nano dispersion liquid and 0.5-0.9% of zinc porphyrin into the solution, wherein the mass fraction of silver nano in the silver nano dispersion liquid is 0.1%, the purity of zinc porphyrin is 98%, reacting for 1-2 hours at the rotating speed of 120-150r/min, centrifuging, washing the product with deionized water for three times, and calcining to obtain the product
Fe3O4/SiO2/TiO2-AgNPs/ZnTPPS。
2. The method for preparing high-performance recyclable photocatalytic magnetic nano-material according to claim 1, wherein in the step (1), the specific operation of preparing magnetic nano-ferroferric oxide is as follows: dissolving ferric chloride hexahydrate and ferrous sulfate heptahydrate in deionized water, introducing nitrogen for 30min at the rotating speed of 100r/min to remove oxygen in the solution, heating the mixed solution to 30 ℃, adding ammonia water into the mixed solution, adjusting the pH of the mixed solution to 10, continuing introducing nitrogen, stirring the mixed solution at the speed of 100r/min to react for 30min, adding sodium citrate accounting for 15% of the mass of the ferric chloride hexahydrate into the mixed solution, heating the mixture to 70 ℃, stirring the mixed solution at the speed of 500r/min to react for 3h, centrifuging, washing the precipitate with ethanol for three times, and then washing with deionized water for three times to obtain the magnetic nano ferroferric oxide.
3. The method for preparing high-performance recyclable photocatalytic magnetic nanomaterial according to claim 1, wherein in the step (5), the silver nano dispersion is prepared by the following method: weighing 0.1558 parts of sodium citrate by weight, dissolving in 3 parts of ultrapure water for later use, and weighing 0.018 part of AgNO3Dissolving the silver nano dispersion in 100 parts of ultrapure water, heating the solution to boiling by using a heating sleeve at the rotating speed of 100r/min, then quickly adding the prepared sodium citrate solution, reacting for 3min, starting to turn yellow, gradually deepening the color of the solution to turn brown yellow, finally turning green, continuing to react for 1h, stopping the reaction, and centrifuging the obtained product by using a centrifugal machine, wherein the supernatant is the silver nano dispersion.
4. The method as claimed in claim 1, wherein in the step (5), the temperature of the calcination treatment is 490-510 ℃, and the time of the calcination treatment is 50-70 min.
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