CN108043433B - Tristannic oxide/silver phosphate composite material photocatalyst and preparation method thereof - Google Patents
Tristannic oxide/silver phosphate composite material photocatalyst and preparation method thereof Download PDFInfo
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- 229910000161 silver phosphate Inorganic materials 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 16
- 229940019931 silver phosphate Drugs 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 80
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 29
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 22
- 239000010452 phosphate Substances 0.000 claims abstract description 22
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000002077 nanosphere Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001119 stannous chloride Substances 0.000 claims abstract description 12
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000001509 sodium citrate Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 7
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 235000021317 phosphate Nutrition 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 8
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 150000003378 silver Chemical class 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 239000002127 nanobelt Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910006702 SnO2-x Inorganic materials 0.000 description 1
- 230000003872 anastomosis Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- -1 is consumed Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- 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
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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
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J35/396—Distribution of the active metal ingredient
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- Organic Chemistry (AREA)
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Abstract
The invention relates to a stannic oxide/silver phosphate composite material photocatalyst and a preparation method thereof. It is flower-shaped Sn3O4Carrying Ag3PO4Structure of nanosphere composed of flower-like Sn3O4In-situ growth of Ag on surfaces3PO4And nanospheres. The preparation method comprises the steps of dissolving trisodium citrate in stannous chloride solution, adding alkali solution into the solution, stirring the solution, transferring the solution into a high-pressure reaction kettle, carrying out hydrothermal reaction, and naturally cooling the solution to room temperature to obtain Sn3O4Material of Sn3O4Ultrasonically dispersing the material in deionized water, and mixing silver salt solution with Sn3O4Mixing the dispersion, and slowly adding the phosphate solution into the silver salt solution and Sn dropwise3O4And (3) drying the dispersion mixed solution at the temperature of 60-80 ℃ for 6-12 h after reaction to obtain the catalyst. The method has the advantages of simple steps, easy control, good visible light catalysis effect of the product and good stability.
Description
Technical Field
The invention relates to a stannic oxide/silver phosphate composite material photocatalyst and a preparation method thereof, belonging to the technical field of catalysts.
Background
With the progress of scientific technology and the rapid development of modern industry, human beings also face significant challenges of environmental pollution and energy shortage. The semiconductor photocatalysis technology directly utilizes solar energy to degrade organic pollutants, has the advantages of environmental protection, sustainable use and the like, has important significance and application prospect in environmental purification, and develops the efficient semiconductor photocatalyst with visible light effect to become the key in the photocatalysis field.
n-type semiconductor oxide SnO2Generally, the material is in a rutile structure, and has a wide application prospect in the fields of catalysts, solar cells, sensors, optoelectronic devices and the like. While SnO2-x(0 < x < 1) is a class of oxides having intermediate valence states and non-stoichiometric ratios, which exhibit some very peculiar physical and chemical properties due to the presence of oxygen vacancies and have gained increasing attention in recent years. Wherein Sn3O4The band gap is about 2.5eV, the photocatalyst has visible light absorption performance, is a novel visible light excited semiconductor photocatalyst, has no toxic or side effect and rich mineral sources, and therefore, the photocatalyst has great application prospects in the aspects of electric conductivity, gas sensitivity, catalytic property and the like. Chinese patent (application number: 201410572875.9) proposes a titanium dioxide nano-belt photocatalytic composite material attached with fish-scale stannic oxide and a preparation method thereof, and the titanium dioxide nano-belt photocatalytic composite material attached with TiO is prepared2Flake Sn on nanobelts3O4The composite catalyst has good catalytic activity. Chinese patent (ZL201110075281.3) proposes Sn3O4Preparation method of nano powder to obtain irregular Sn3O4And (3) nanoparticles. But due to Sn3O4The generated photo-generated electrons and holes are easy to recombine, the service life of a photo-generated carrier is short, and the catalytic activity of the photo-generated carrier is low, so that how to improve the catalytic activity of the photo-generated carrier under visible light radiation becomes a focus of attention.
In 2010, the research group of the leaf golden flower reports Ag for the first time3PO4The semiconductor catalyst has visible light catalytic activity and has great prospect in the aspects of oxygen generation by water photolysis and organic dye photocatalytic degradation. However, pure Ag was prepared3PO4A large amount of silver, which is a noble metal, is consumed, and Ag3PO4Has poor self chemical stability, is easy to be decomposed into silver simple substance due to photo corrosion to reduce the catalytic activity, thereby reducing Ag3PO4The cost and the stability are improved, and the research focus of the system is at present. The research finds that the flower-shaped structure Sn is not found in the current research results3O4Carrying Ag3PO4The related report of composite photocatalyst.
Disclosure of Invention
In view of the above, the present invention provides a flower-shaped Sn3O4Carrying Ag3PO4A method for preparing a novel composite visible light photocatalyst of nanospheres.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the composite material photocatalyst of stannic oxide and silver phosphate is flower-shaped Sn3O4Carrying Ag3PO4Structure of nanosphere composed of flower-like Sn3O4In-situ growth of Ag on surfaces3PO4And (4) nanospheres. The flower-shaped Sn3O4The Ag is stacked by sheets with a thickness of 50-100 nm to form a flower-like structure3PO4The particle size of the nanospheres is 40-70 nm.
A preparation method of a stannic oxide/silver phosphate composite photocatalyst comprises the following steps:
(1) adding 1-5 g SnCl2·2H2Dissolving O in 20-60 mL of deionized water, stirring for 10-30 min to obtain a stannous chloride solution, dissolving 2-10 g of trisodium citrate in the stannous chloride solution, stirring for 10-30 min to obtain a mixed solution, adding 20-50 mL of 0.05-0.5M aqueous alkali into the mixed solution, and stirring for 10-30 min;
(2) transferring the solution obtained in the step (1) into a high-pressure reaction kettle, carrying out hydrothermal reaction at 120-200 ℃ for 12-24 h, naturally cooling to room temperature, filtering, centrifugally separating, washing with absolute ethyl alcohol for 3-5 times, and drying at 60-80 ℃ for 6-12 h to obtain Sn3O4A material;
(3) sn obtained in the step (2)3O4The material is ultrasonically dispersed in 50-100 mL of deionized water, silver salt is dissolved in 20-50 mL of deionized water, the mixture is stirred for 10-30 min at room temperature under the condition of keeping out of the sun to obtain silver salt solution, and the silver salt solution and Sn are mixed3O4Mixing the dispersion solutions, and stirring for 30-60 min at room temperature in a dark condition to obtain a first solution;
(4) dissolving 20-80 g of phosphate in 10-50 mL of deionized water, stirring at room temperature for 10-30 min to obtain a phosphate solution, dropwise and slowly adding the phosphate solution into the first solution obtained in the step (3), and continuing to react at room temperature in a dark place after dropwise addition;
(5) and (3) filtering the reaction product obtained in the step (4), performing centrifugal separation, washing with absolute ethyl alcohol for 3-5 times, and drying at 60-80 ℃ for 6-12 hours to obtain the catalyst.
And (2) in the step (1), the alkali solution is sodium hydroxide or potassium hydroxide solution.
The silver salt in the step (3) is AgNO3Or CH3COOAg, the phosphate in the step (4) is Na3PO4Or Na2HPO4Ag/PO in silver salts and phosphates4 3-Is 3: 1.
Ag/Sn in the first solution in the step (3)3O4The molar ratio of (A) to (B) is 5:1 to 50: 1.
And (4) reacting for 2-3h at room temperature in a dark condition.
Reacting trisodium citrate with stannous chloride through hydrothermal reaction under alkaline condition to obtain flower-shaped Sn3O4Then Sn is added3O4Dispersing into water, adding silver salt solution, dripping phosphate solution, reacting at room temperature to obtain Sn3O4/Ag3PO4The invention has simple process and realizes Ag3PO4Nanoparticles in Sn3O4And growing the surface in situ.
The invention has the beneficial effects that: sn provided by the invention3O4/Ag3PO4The composite photocatalyst has good visible light catalysis effect and is stableGood in performance, by introducing Ag3PO4At Sn3O4Surface in-situ growth of Ag3PO4Obtaining Sn from nanoparticles3O4/Ag3PO4The composite photocatalyst has simple steps, is easy to control, saves the consumption of noble metal silver and reduces the production cost.
Drawings
FIG. 1 shows flower-like Sn prepared in example 1 of the present invention3O4Field Emission Scanning Electron Microscopy (FESEM) images of (a).
FIG. 2 shows Sn prepared in example 1 of the present invention3O4/Ag3PO4Field Emission Scanning Electron Microscopy (FESEM) images of (a).
FIG. 3 shows flower-like Sn prepared in example 1 of the present invention3O4X-ray diffraction (XRD) pattern of (a).
FIG. 4 shows Sn prepared in example 1 of the present invention3O4/Ag3PO4X-ray diffraction (XRD) pattern of (a).
FIG. 5 shows Sn prepared in example 1 of the present invention3O4And Sn3O4/Ag3PO4The composite material has the catalytic performance of degrading methylene blue under the catalysis of visible light. Wherein a is Sn3O4B is Sn prepared in example 13O4/Ag3PO4Degradation profile of the composite.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings and examples.
The composite material photocatalyst of stannic oxide and silver phosphate is flower-shaped Sn3O4Carrying Ag3PO4Structure of nanosphere composed of flower-like Sn3O4In-situ growth of Ag on surfaces3PO4Nanospheres of said flower-like Sn3O4The Ag is stacked by sheets with a thickness of 50-100 nm to form a flower-like structure3PO4The particle size of the nanospheres is 40-70 nm.
A preparation method of a stannic oxide/silver phosphate composite photocatalyst comprises the following steps:
(1) adding 1-5 g SnCl2·2H2Dissolving O in 20-60 mL of deionized water, stirring for 10-30 min to obtain a stannous chloride solution, dissolving 2-10 g of trisodium citrate in the stannous chloride solution, stirring for 10-30 min to obtain a mixed solution, adding 20-50 mL of 0.05-0.5M aqueous alkali into the mixed solution, and stirring for 10-30 min;
(2) transferring the solution obtained in the step (1) into a high-pressure reaction kettle, carrying out hydrothermal reaction at 120-200 ℃ for 12-24 h, naturally cooling to room temperature, filtering, centrifugally separating, washing with absolute ethyl alcohol for 3-5 times, and drying at 60-80 ℃ for 6-12 h to obtain Sn3O4A material;
(3) sn obtained in the step (2)3O4The material is ultrasonically dispersed in 50-100 mL of deionized water, silver salt is dissolved in 20-50 mL of deionized water, the mixture is stirred for 10-30 min at room temperature under the condition of keeping out of the sun to obtain silver salt solution, and the silver salt solution and Sn are mixed3O4Mixing the dispersion solutions, and stirring for 30-60 min at room temperature in a dark condition to obtain a first solution;
(4) dissolving 20-80 g of phosphate in 10-50 mL of deionized water, stirring at room temperature for 10-30 min to obtain a phosphate solution, dropwise and slowly adding the phosphate solution into the first solution obtained in the step (3), and continuing to react at room temperature in a dark place after dropwise addition;
(5) and (3) filtering the reaction product obtained in the step (4), performing centrifugal separation, washing with absolute ethyl alcohol for 3-5 times, and drying at 60-80 ℃ for 6-12 hours to obtain the catalyst.
And (2) in the step (1), the alkali solution is sodium hydroxide or potassium hydroxide solution.
The silver salt in the step (3) is AgNO3Or CH3COOAg, the phosphate in the step (4) is Na3PO4Or Na2HPO4Ag/PO in silver salts and phosphates4 3-Is 3: 1.
Ag/Sn in the first solution in the step (3)3O4The molar ratio of (A) to (B) is 5:1 to 50: 1.
And (4) reacting for 2-3h at room temperature in a dark condition.
Example 1
(1) Adding 1.128g SnCl2·2H2Dissolving O in 15mL of deionized water, and stirring for 30 min;
(2) 3.368g trisodium citrate (Na)3C6H5O7·2H2O) is dissolved in the solution obtained in the step (1) and stirred for 20 min;
(3) adding 20mL of 0.2M NaOH solution into the solution obtained in the step (1), and stirring for 30 min;
(4) and (4) transferring the solution obtained in the step (3) to a high-pressure reaction kettle, preserving the temperature for 15h at 180 ℃, and naturally cooling to room temperature.
(5) Filtering the reaction product, centrifuging, washing with anhydrous ethanol for 3 times, and drying at 60 deg.C for 12 hr to obtain Sn3O4A material.
(6) Weighing 1.26g of Sn obtained in the step (5)3O4The material, dispersed in 50mL deionized water, sonicated for 20 min.
(7) 0.306g of AgNO3Dissolving in 20mL deionized water, and stirring for 30min at room temperature in a dark place;
(8) adding the solution obtained in the step (7) into the solution obtained in the step (6), and stirring for 30min at room temperature in a dark condition;
(9) mixing 0.215gNa2HPO4·12H2Dissolving O in 10mL of deionized water, and stirring at room temperature for 30 min;
(10) dropwise and slowly adding the solution obtained in the step (9) into the solution obtained in the step (8), and stirring for 60min at room temperature in a dark place;
(11) filtering the reaction product, centrifuging, washing with anhydrous ethanol for 3 times, and drying at 60 deg.C for 12 h.
FIGS. 1 and 3 show flower-like Sn obtained in this example3O4Scanning Electron Microscopy (FESEM) and X-ray diffraction (XRD) patterns. As can be seen from FIG. 1, the flower-like Sn prepared in step (3) of the present invention3O4A material. Wherein the flower is formed by clustering lamellar layers, and the thickness of the lamellar layers is 50-100 nm. As can be seen from FIG. 3, Sn prepared in step (3) of the present invention3O4The crystal structure and the card number are No.16-0737, anastomosis.
FIGS. 2 and 4 show Sn obtained in this example3O4/Ag3PO4Field Emission Scanning Electron Microscopy (FESEM) and X-ray diffraction (XRD) patterns of the composite photocatalyst. As can be seen from FIG. 2, the composite photocatalyst prepared by the method is composed of flower-shaped Sn3O4In situ growth of Ag3PO4Is formed of particles of Ag3PO4The particle size of the particles is 40-60 nm. Due to Sn3O4Thin layer, Ag3PO4The insertion of the particles will partially destroy Sn3O4The flower-like structure of (1). Due to Ag3PO4Small particle loading, Sn of FIG. 43O4/Ag3PO4In the XRD pattern of the composite photocatalyst, part of Ag is observed3PO4And the diffraction peak intensity is weak.
Sn prepared by the invention3O4/Ag3PO4And carrying out a photocatalytic degradation methyl blue experiment on the composite photocatalyst. The specific test method comprises the following steps:
30mg of sample was added to a 250mL quartz tube with 10mg/L methylene blue solution. Stirring for 30min under dark conditions to reach adsorption equilibrium. And turning on a 300W xenon lamp, keeping stirring, and performing visible light photocatalytic degradation. The solution was taken every 15min, centrifuged, separated and the absorbance of the supernatant tested. At the same time with Sn3O4As a control test. The degradation rate of the catalyst to methylene blue is calculated according to the following formula:
in the formula, C, C0The absorbance of methylene blue before and after degradation, respectively.
FIG. 5 shows Sn prepared by the present invention3O4/Ag3PO4Composite photocatalyst and control sample Sn3O4Degradation profile of the photocatalyst under visible light conditions for methylene blue. As shown in FIG. 5(a), pure Sn is used3O4Is photo-catalyzedWhen the agent is used, methylene blue cannot be completely degraded after 60 min. As can be seen from FIG. 5(b), Sn3O4/Ag3PO4The composite photocatalyst can completely degrade methylene blue after 60min, and indicates Sn3O4With Ag3PO4The compounded sample has good visible light catalytic performance.
Example 2
(1) Adding 1.128g SnCl2·2H2Dissolving O in 15mL of deionized water, and stirring for 30 min;
(2) 3.368g of trisodium citrate Na3C6H5O7·2H2Dissolving O in the solution obtained in the step (1), and stirring for 20 min;
(3) adding 20mL of 0.2M NaOH solution into the solution obtained in the step (1), and stirring for 30 min;
(4) and (4) transferring the solution obtained in the step (3) to a high-pressure reaction kettle, preserving the temperature for 15h at 180 ℃, and naturally cooling to room temperature.
(5) Filtering the reaction product, centrifuging, washing with anhydrous ethanol for 3 times, and drying at 60 deg.C for 12 hr to obtain Sn3O4A material.
(6) Weighing 2.52g of Sn obtained in the step (5)3O4The material, dispersed in 50mL deionized water, sonicated for 20 min.
(7) 0.306g of AgNO3Dissolving in 20-50 mL of deionized water, and stirring for 30min at room temperature in a dark condition;
(8) adding the solution obtained in the step (7) into the solution obtained in the step (6), and stirring for 30min at room temperature in a dark condition;
(9) 0.098g of Na3PO4·12H2Dissolving O in 40mL of deionized water, and stirring at room temperature for 30 min;
(10) dropwise and slowly adding the solution obtained in the step (9) into the solution obtained in the step (8), and stirring for 60min at room temperature in a dark place;
(11) filtering the reaction product, centrifuging, washing with anhydrous ethanol for 3 times, and drying at 60 deg.C for 12 h.
Example 3
Tristannic oxide/silver phosphate composite material photocatalystIt is flower-shaped Sn3O4Carrying Ag3PO4Structure of nanosphere composed of flower-like Sn3O4In-situ growth of Ag on surfaces3PO4Nanospheres of said flower-like Sn3O4The Ag is stacked by sheets with a thickness of 50-100 nm to form a flower-like structure3PO4The particle size of the nanospheres is 40-70 nm.
A preparation method of a stannic oxide/silver phosphate composite photocatalyst comprises the following steps:
(1) 2.5g SnCl2·2H2Dissolving O in 40mL of deionized water, stirring for 22min to obtain a stannous chloride solution, dissolving trisodium citrate in the stannous chloride solution, stirring for 20min to obtain a mixed solution, adding 40mL of 0.15M aqueous alkali into the mixed solution, and stirring for 20 min;
(2) transferring the solution obtained in the step (1) into a high-pressure reaction kettle, carrying out hydrothermal reaction at 155 ℃ for 20h, naturally cooling to room temperature, filtering the reaction product, carrying out centrifugal separation, washing with absolute ethyl alcohol for 4 times, and drying at 68 ℃ for 8h to obtain Sn3O4A material;
(3) sn obtained in the step (2)3O4The material is ultrasonically dispersed in 80mL deionized water, silver salt is dissolved in 40mL deionized water, the mixture is stirred for 20min under the condition of room temperature and light shielding to obtain silver salt solution, and the silver salt solution and Sn are mixed3O4Mixing the dispersion solutions, and stirring for 40min at room temperature in a dark condition to obtain a first solution;
(4) dissolving phosphate in 40mL of deionized water, stirring at room temperature for 20min to obtain a phosphate solution, dropwise and slowly adding the phosphate solution into the first solution obtained in the step (3), and continuing to react at room temperature in a dark condition after dropwise addition;
(5) and (3) filtering the reaction product obtained in the step (4), performing centrifugal separation, washing with absolute ethyl alcohol for 5 times, and drying at 75 ℃ for 10 hours to obtain the catalyst.
And (2) in the step (1), the alkali solution is a potassium hydroxide solution.
The silver salt in the step (3) is CH3COOAg, the phosphate in the step (4) is Na3PO4Ag in silver salts and phosphates/PO4 3-Is 3: 1.
Ag/Sn in the first solution in the step (3)3O4Is 8: 1.
And (3) in the step (4), the reaction time is 2.5h under the condition of room temperature and light shielding.
Example 4
The composite material photocatalyst of stannic oxide and silver phosphate is flower-shaped Sn3O4Carrying Ag3PO4Structure of nanosphere composed of flower-like Sn3O4In-situ growth of Ag on surfaces3PO4Nanospheres of said flower-like Sn3O4The Ag is stacked by sheets with a thickness of 50-100 nm to form a flower-like structure3PO4The particle size of the nanospheres is 40-70 nm.
A preparation method of a stannic oxide/silver phosphate composite photocatalyst comprises the following steps:
(1) adding 3g SnCl2·2H2Dissolving O in 30mL of deionized water, stirring for 15min to obtain a stannous chloride solution, dissolving trisodium citrate in the stannous chloride solution, stirring for 25min to obtain a mixed solution, adding 40mL of 0.2M aqueous alkali into the mixed solution, and stirring for 15 min;
(2) transferring the solution obtained in the step (1) into a high-pressure reaction kettle, carrying out hydrothermal reaction at 185 ℃ for 20h, naturally cooling to room temperature, filtering the reaction product, carrying out centrifugal separation, washing with absolute ethyl alcohol for 3 times, and drying at 75 ℃ for 8h to obtain Sn3O4A material;
(3) sn obtained in the step (2)3O4The material is ultrasonically dispersed in 85mL deionized water, silver salt is dissolved in 40mL deionized water, the mixture is stirred for 25min under the condition of room temperature and light shielding to obtain silver salt solution, and the silver salt solution and Sn are mixed3O4Mixing the dispersion solutions, and stirring for 45min at room temperature in a dark condition to obtain a first solution;
(4) dissolving phosphate in 20mL of deionized water, stirring at room temperature for 15min to obtain a phosphate solution, dropwise and slowly adding the phosphate solution into the first solution obtained in the step (3), and continuing to react at room temperature in a dark condition after dropwise addition;
(5) and (3) filtering the reaction product obtained in the step (4), performing centrifugal separation, washing with absolute ethyl alcohol for 5 times, and drying at 75 ℃ for 10 hours to obtain the catalyst.
And (2) in the step (1), the alkali solution is a sodium hydroxide solution.
The silver salt in the step (3) is AgNO3In the step (4), the phosphate is Na2HPO4Ag/PO in silver salts and phosphates4 3-Is 3: 1.
Ag/Sn in the first solution in the step (3)3O4Is 10: 1.
And (3) in the step (4), the reaction time is 2.5h under the condition of room temperature and light shielding.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (3)
1. The preparation method of the stannic oxide/silver phosphate composite photocatalyst is characterized in that the stannic oxide/silver phosphate composite photocatalyst is flower-shaped Sn3O4Carrying Ag3PO4Structure of nanosphere composed of flower-like Sn3O4In-situ growth of Ag on surfaces3PO4Nanospheres of said flower-like Sn3O4The Ag is stacked by sheets with a thickness of 50-100 nm to form a flower-like structure3PO4The particle size of the nanospheres is 40-70 nm, and the preparation method comprises the following steps:
(1) adding 1-5 g SnCl2·2H2Dissolving O in 20-60 mL of deionized water, stirring for 10-30 min to obtain a stannous chloride solution, dissolving 2-10 g of trisodium citrate in the stannous chloride solution, stirring for 10-30 min to obtain a mixed solution, adding 20-50 mL of 0.05-0.5M aqueous alkali into the mixed solution, and stirring for 10-30 min;
(2) transferring the solution obtained in the step (1) into a high-pressure reaction kettle, carrying out hydrothermal reaction at 120-200 ℃ for 12-24 h, naturally cooling to room temperature, filtering, centrifugally separating, washing with absolute ethyl alcohol for 3-5 times, and drying at 60-80 ℃ for 6-12 h to obtain Sn3O4A material;
(3) sn obtained in the step (2)3O4The material is ultrasonically dispersed in 50-100 mL of deionized water, silver salt is dissolved in 20-50 mL of deionized water, the mixture is stirred for 10-30 min at room temperature under the condition of keeping out of the sun to obtain silver salt solution, and the silver salt solution and Sn are mixed3O4Mixing the dispersion solutions, and stirring for 30-60 min at room temperature in a dark condition to obtain a first solution;
(4) dissolving 20-80 g of phosphate in 10-50 mL of deionized water, stirring at room temperature for 10-30 min to obtain a phosphate solution, dropwise and slowly adding the phosphate solution into the first solution obtained in the step (3), and continuing to react at room temperature in a dark place after dropwise addition;
(5) filtering the reaction product obtained in the step (4), performing centrifugal separation, washing with absolute ethyl alcohol for 3-5 times, and drying at 60-80 ℃ for 6-12 hours to obtain the catalyst;
wherein Ag/Sn is contained in the first solution in the step (3)3O4In a molar ratio of 10: 1;
the silver salt in the step (3) is AgNO3Or CH3COOAg, the phosphate in the step (4) is Na3PO4Or Na2HPO4Ag/PO in silver salts and phosphates4 3-Is 3: 1.
2. The method for preparing the stannic oxide/silver phosphate composite photocatalyst according to claim 1, wherein the alkali solution in the step (1) is sodium hydroxide or potassium hydroxide solution.
3. The preparation method of the stannic oxide/silver phosphate composite photocatalyst of claim 1, wherein the reaction time in the step (4) is 2-3h at room temperature under a dark condition.
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| Ag3PO4/SnO2 semiconductor nanocomposites with enhanced photocatalytic activity and stability;Lili Zhang等;《New J. Chem.》;20120511;第36卷;3790-3793页 * |
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