CN108043433A - One kind four aoxidizes three tin/silver orthophosphate composite material photocatalyst and preparation method thereof - Google Patents
One kind four aoxidizes three tin/silver orthophosphate composite material photocatalyst and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 19
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 36
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 34
- 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 27
- 239000010452 phosphate Substances 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 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000002077 nanosphere Substances 0.000 claims abstract description 17
- 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
- 229910021626 Tin(II) chloride Inorganic materials 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
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000001509 sodium citrate Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 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 7
- 239000012467 final product Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003643 water by type Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 235000019263 trisodium citrate Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 101710134784 Agnoprotein Proteins 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229940038773 trisodium citrate Drugs 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 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
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 235000005979 Citrus limon Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 229910006702 SnO2-x Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 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
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- 229910000406 trisodium phosphate Inorganic materials 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
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
- 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
-
- 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
-
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to one kind four to aoxidize three tin/silver orthophosphate composite material photocatalyst and preparation method thereof.It is flower-shaped Sn3O4Loaded Ag3PO4The structure of nanosphere, by flower-shaped Sn3O4Growth in situ Ag on surface3PO4Nanosphere forms.Its preparation method is that trisodium citrate is dissolved in stannous chloride solution, and aqueous slkali is added thereto, is moved to after stirring in autoclave, and hydro-thermal reaction, cooled to room temperature obtains Sn3O4Material, by Sn3O4Material ultrasonic disperse in deionized water, by silver salt solution and Sn3O4Dispersion liquid mixes, and phosphate solution is slowly added to silver salt solution and Sn dropwise3O4In dispersion liquid mixed solution, after reaction in 60~80 DEG C of dry 6~12h to obtain the final product.Step of the present invention is simple, is easy to control, and product has good visible light catalytic effect, and stability is good.
Description
Technical field
The present invention relates to one kind four to aoxidize three tin/silver orthophosphate composite material photocatalyst and preparation method thereof, belongs to catalysis
Agent technical field.
Background technology
With the progress of science and technology and the rapid development of modern industry, the mankind are also faced with environmental pollution and energy shortage
Significant challenge.Photocatalitic Technique of Semiconductor degrades to organic pollution directly using solar energy, have it is environmentally protective,
The advantages that sustainable use, is beneficial to be of great significance and application prospect in the depollution of environment, and develops efficient visible luminous effect
Semiconductor light-catalyst become photocatalysis field key.
N-type semiconductor oxide S nO2Usually rutile structure, in catalyst, solar cell, sensor, photoelectricity
The fields such as sub- device show wide application prospect.And SnO2-x(0 ＜ x ＜ 1) is a kind of with intermediate valence state and non-chemical
Measure ratio oxide, due to the presence of Lacking oxygen, some very peculiar physics and chemical characteristic can be shown, in recent years by
Gradually people is subject to pay close attention to.Wherein Sn3O4Band gap is about 2.5eV, has visible absorption performance, is that a kind of new visible ray swashs
Semiconductor light-catalyst is sent out, has no toxic side effect and mineral resources is enriched, therefore in the side such as electric conductivity, gas-sensitive property and catalysis characteristics
Face has great application prospect.Chinese patent (application number：201410572875.9) propose a kind of attachment four oxygen of fish scale-shaped
Change the titanium dioxide nano-belts optic catalytic composite material and preparation method of three tin, which is prepared for being attached to TiO2Nanobelt
On flakey Sn3O4, the composite catalyst is with good catalytic activity.Chinese patent (ZL201110075281.3) proposes
A kind of Sn3O4The preparation method of nano-powder has obtained irregular Sn3O4Nano particle.But due to Sn3O4The light of middle generation
Raw electron-hole is easily compound, and photo-generated carrier short life causes its catalytic activity not high, therefore how to improve it visible
Catalytic activity under light radiation becomes the focus of attention.
2010, leaf golden flower research groups reported Ag for the first time3PO4Semiconductor catalyst has visible light catalysis activity,
Great prospect in terms of photocatalytic water oxygen and photocatalytically degradating organic dye.However prepare pure Ag3PO4Your substantial amounts of gold of consumption needed
Belong to elemental silver, and Ag3PO4Itself poor chemical stability easily reduces its catalytic activity due to photoetch is decomposed into silver-colored simple substance, because
This reduces Ag3PO4Cost improves the research hotspot that its stability is the current system.Retrieval is found, in current achievement in research
It has not been found that flower-like structure Sn3O4Loaded Ag3PO4The relevant report of composite photo-catalyst.
The content of the invention
In view of this, the present invention provides a kind of flower-shaped Sn3O4Loaded Ag3PO4The NEW TYPE OF COMPOSITE visible light catalytic of nanosphere
The preparation method of agent.
The technical solution adopted by the present invention to solve the technical problems is：
One kind four aoxidizes three tin/silver orthophosphate composite material photocatalyst, is flower-shaped Sn3O4Loaded Ag3PO4Nanosphere
Structure, by flower-shaped Sn3O4Growth in situ Ag on surface3PO4Nanosphere is formed.The flower-shaped Sn3O4It is 50~100nm's by thickness
Thin slice is accumulated and forms flower-like structure, the Ag3PO4The grain size of nanosphere is 40~70nm.
A kind of preparation method of four oxidations, three tin/silver orthophosphate composite material photocatalyst, is following steps：
(1) by 1~5gSnCl2·2H2O is dissolved in 20~60mL deionized waters, and 10~30min of stirring obtains stannous chloride
2~10g trisodium citrates are dissolved in stannous chloride solution by solution, and 10~30min of stirring obtains mixed solution, by 20~
50mL concentration is added in for 0.05~0.5M aqueous slkalis in mixed solution, stirs 10~30min；
(2) step (1) acquired solution is transferred in autoclave, in 120~200 DEG C of hydro-thermal reactions 12~for 24 hours, from
It is so cooled to room temperature, reaction product is filtered, is centrifuged, washes of absolute alcohol 3~5 times, in 60~80 DEG C of dry 6~12h,
Obtain Sn3O4Material；
(3) Sn for obtaining step (2)3O4Material, ultrasonic disperse are dissolved in 20 in 50~100mL deionized waters, by silver salt
In~50mL deionized waters, 10~30min of stirring obtains silver salt solution under the conditions of room temperature is protected from light, by silver salt solution and Sn3O4
Dispersion liquid mixes, and 30~60min is stirred under the conditions of room temperature is protected from light and obtains the first solution；
(4) 20~80g phosphate is dissolved in 10~50mL deionized waters, stirs 10~30min at room temperature and obtain phosphoric acid
Phosphate solution is slowly added in the first solution obtained by step (3), item is protected from light in room temperature after being added dropwise by salting liquid dropwise
The reaction was continued under part；
(5) by the filtering of step (4) reaction product, centrifuge, washes of absolute alcohol 3~5 times, at 60~80 DEG C dry 6
~12h to obtain the final product.
Aqueous slkali is sodium hydroxide or potassium hydroxide solution in the step (1).
Silver salt is AgNO in the step (3)3Or CH3COOAg, phosphate is Na in the step (4)3PO4Or
Na2HPO4, Ag/PO in silver salt and phosphate4 3-Molar ratio be 3:1.
Ag/Sn in first solution in the step (3)3O4Molar ratio be 5:1~50:1.
The reaction time is 2-3h under the conditions of room temperature is protected from light in the step (4).
In alkaline conditions, by hydro-thermal reaction, trisodium citrate and stannous chloride is reacted, obtain flower-shaped Sn3O4, so
Afterwards by Sn3O4It is distributed in water, adds silver salt solution, then phosphate solution is added dropwise, then Sn is obtained by the reaction at room temperature3O4/
Ag3PO4Composite photo-catalyst, present invention process is simple, and realizes Ag3PO4Nano particle is in Sn3O4Surface in situ is grown.
Beneficial effects of the present invention are：Sn provided by the invention3O4/Ag3PO4Composite photo-catalyst has good visible
Photocatalysis effect, and stability is good, by introducing Ag3PO4, in Sn3O4Surface in situ grows Ag3PO4Nano particle obtains Sn3O4/
Ag3PO4Composite photo-catalyst, step is simple, is easy to control, and saves the consumption of noble silver, reduces production cost.
Description of the drawings
Flower-shaped Sn standby for the embodiment of the present invention 1 Fig. 13O4Field emission scanning electron microscope (FESEM) figure.
Sn standby for the embodiment of the present invention 1 Fig. 23O4/Ag3PO4Field emission scanning electron microscope (FESEM) figure.
Flower-shaped Sn standby for the embodiment of the present invention 1 Fig. 33O4X-ray diffraction (XRD) figure.
Sn standby for the embodiment of the present invention 1 Fig. 43O4/Ag3PO4X-ray diffraction (XRD) figure.
Sn standby for the embodiment of the present invention 1 Fig. 53O4With Sn3O4/Ag3PO4Composite material visible light photocatalytic degradation methylene
Blue catalytic performance.Wherein a is Sn3O4Degradation curve figure, b is the Sn prepared in embodiment 13O4/Ag3PO4Composite material
Degradation curve figure.
Specific embodiment
Presently in connection with drawings and examples, specifically the present invention is described in further detail.
One kind four aoxidizes three tin/silver orthophosphate composite material photocatalyst, is flower-shaped Sn3O4Loaded Ag3PO4Nanosphere
Structure, by flower-shaped Sn3O4Growth in situ Ag on surface3PO4Nanosphere forms, the flower-shaped Sn3O4It is 50~100nm's by thickness
Thin slice is accumulated and forms flower-like structure, the Ag3PO4The grain size of nanosphere is 40~70nm.
A kind of preparation method of four oxidations, three tin/silver orthophosphate composite material photocatalyst, is following steps：
(1) by 1~5gSnCl2·2H2O is dissolved in 20~60mL deionized waters, and 10~30min of stirring obtains stannous chloride
2~10g trisodium citrates are dissolved in stannous chloride solution by solution, and 10~30min of stirring obtains mixed solution, by 20~
The aqueous slkali that 50mL concentration is 0.05~0.5M is added in mixed solution, stirs 10~30min；
(2) step (1) acquired solution is transferred in autoclave, in 120~200 DEG C of hydro-thermal reactions 12~for 24 hours, from
It is so cooled to room temperature, reaction product is filtered, is centrifuged, washes of absolute alcohol 3~5 times, in 60~80 DEG C of dry 6~12h,
Obtain Sn3O4Material；
(3) Sn for obtaining step (2)3O4Material, ultrasonic disperse are dissolved in 20 in 50~100mL deionized waters, by silver salt
In~50mL deionized waters, 10~30min of stirring obtains silver salt solution under the conditions of room temperature is protected from light, by silver salt solution and Sn3O4
Dispersion liquid mixes, and 30~60min is stirred under the conditions of room temperature is protected from light and obtains the first solution；
(4) 20~80g phosphate is dissolved in 10~50mL deionized waters, stirs 10~30min at room temperature and obtain phosphoric acid
Phosphate solution is slowly added in the first solution obtained by step (3), item is protected from light in room temperature after being added dropwise by salting liquid dropwise
The reaction was continued under part；
(5) by the filtering of step (4) reaction product, centrifuge, washes of absolute alcohol 3~5 times, at 60~80 DEG C dry 6
~12h to obtain the final product.
Aqueous slkali is sodium hydroxide or potassium hydroxide solution in the step (1).
Silver salt is AgNO in the step (3)3Or CH3COOAg, phosphate is Na in the step (4)3PO4Or
Na2HPO4, Ag/PO in silver salt and phosphate4 3-Molar ratio be 3:1.
Ag/Sn in first solution in the step (3)3O4Molar ratio be 5:1~50:1.
The reaction time is 2-3h under the conditions of room temperature is protected from light in the step (4).
Embodiment 1
(1) by 1.128gSnCl2·2H2O is dissolved in 15mL deionized waters, stirs 30min；
(2) by 3.368g trisodium citrates (Na3C6H5O7·2H2O) it is dissolved in step (1) acquired solution, stirs 20min；
(3) NaOH solution that 20mL concentration is 0.2M is added in step (1) acquired solution, stirs 30min；
(4) step (3) acquired solution is transferred in autoclave, 15h, cooled to room temperature is kept the temperature at 180 DEG C.
(5) reaction product filtered, centrifuged, washes of absolute alcohol 3 times, in 60 DEG C of dry 12h, obtaining Sn3O4Material
Material.
(6) Sn that 1.26g steps (5) obtain is weighed3O4Material is dispersed in 50mL deionized waters, ultrasonic 20min.
(7) by 0.306gAgNO3It is dissolved in 20mL deionized waters, 30min is stirred under the conditions of room temperature is protected from light；
(8) step (7) acquired solution is added in into step (6) acquired solution, 30min is stirred under the conditions of room temperature is protected from light；
(9) by 0.215gNa2HPO4·12H2O is dissolved in 10mL deionized waters, stirs 30min at room temperature；
(10) step (9) acquired solution is slowly added to step (8) acquired solution dropwise, is stirred under the conditions of room temperature is protected from light
60min；
(11) reaction product filtered, centrifuged, washes of absolute alcohol 3 times, in 60 DEG C of dry 12h.
Fig. 1 and Fig. 3 is the flower-shaped Sn obtained in the present embodiment3O4Field hair scanning electron microscope (FESEM) and X-ray diffraction
(XRD) figure.It will be seen from figure 1 that it is flower-shaped Sn that step (3) of the present invention, which is prepared,3O4Material.Wherein spend by lamella cluster
It forms, the thickness of lamella is 50~100nm.As seen from Figure 3, the Sn that prepared by step (3) of the present invention3O4Crystal structure and card
Piece number is coincideing for No.16-0737.
Fig. 2 and Fig. 4 is the Sn that the present embodiment obtains3O4/Ag3PO4The field emission scanning electron microscope of composite photo-catalyst
(FESEM) and X-ray diffraction (XRD) figure.Figure it is seen that the composite photo-catalyst prepared by the present invention is by flower-shaped Sn3O4
Growth in situ Ag3PO4Particle forms, Ag3PO4The grain size of particle is 40~60nm.Due to Sn3O4Lamella is relatively thin, Ag3PO4Particle
Insertion can partial destruction Sn3O4Flower-like structure.Due to Ag3PO4Particulate load amount is smaller, the Sn of Fig. 43O4/Ag3PO4It is compound
In the XRD spectrum of photochemical catalyst, part Ag is observed3PO4Diffraction maximum, and diffraction peak intensity is weaker.
Sn prepared by the present invention3O4/Ag3PO4Composite photo-catalyst carries out Methyl blueness experiment.Specific examination
Proved recipe method is：
30mg samples are added in into the quartz ampoule of the methylene blue solution for the 10mg/L for having 250mL.It is stirred under dark condition
It mixes 30min and reaches adsorption equilibrium.300W xenon lamps are opened, and are kept stirring, carry out visible light photocatalytic degradation.Every 15min
A solution is taken, centrifugation separates, and tests the absorbance of supernatant.Simultaneously with Sn3O4For check experiment.Catalyst is to methylene blue
Degradation rate calculated according to the following formula：
In formula, C, C0The absorbance of methylene blue before and after respectively degrading.
Fig. 5 is Sn prepared by the present invention3O4/Ag3PO4Composite photo-catalyst and control sample Sn3O4Photochemical catalyst is in visible ray
Under the conditions of to the degradation curve figure of methylene blue.In Fig. 5 shown in (a), with pure Sn3O4For photochemical catalyst when, through 60min still not
It can degradable methylene blue.The Sn it can be seen from (b) in Fig. 53O4/Ag3PO4Composite photo-catalyst can drop completely through 60min
Methylene blue is solved, shows Sn3O4With Ag3PO4Sample after compound has good visible light catalytic performance.
Embodiment 2
(1) by 1.128gSnCl2·2H2O is dissolved in 15mL deionized waters, stirs 30min；
(2) by 3.368g trisodium citrates Na3C6H5O7·2H2O is dissolved in step (1) acquired solution, stirs 20min；
(3) NaOH solution that 20mL concentration is 0.2M is added in step (1) acquired solution, stirs 30min；
(4) step (3) acquired solution is transferred in autoclave, 15h, cooled to room temperature is kept the temperature at 180 DEG C.
(5) reaction product filtered, centrifuged, washes of absolute alcohol 3 times, in 60 DEG C of dry 12h, obtaining Sn3O4Material
Material.
(6) Sn that 2.52g steps (5) obtain is weighed3O4Material is dispersed in 50mL deionized waters, ultrasonic 20min.
(7) by 0.306gAgNO3It is dissolved in 20~50mL deionized waters, 30min is stirred under the conditions of room temperature is protected from light；
(8) step (7) acquired solution is added in into step (6) acquired solution, 30min is stirred under the conditions of room temperature is protected from light；
(9) by 0.098g Na3PO4·12H2O is dissolved in 40mL deionized waters, stirs 30min at room temperature；
(10) step (9) acquired solution is slowly added to step (8) acquired solution dropwise, is stirred under the conditions of room temperature is protected from light
60min；
(11) reaction product filtered, centrifuged, washes of absolute alcohol 3 times, in 60 DEG C of dry 12h.
Embodiment 3
One kind four aoxidizes three tin/silver orthophosphate composite material photocatalyst, is flower-shaped Sn3O4Loaded Ag3PO4Nanosphere
Structure, by flower-shaped Sn3O4Growth in situ Ag on surface3PO4Nanosphere forms, the flower-shaped Sn3O4It is 50~100nm's by thickness
Thin slice is accumulated and forms flower-like structure, the Ag3PO4The grain size of nanosphere is 40~70nm.
A kind of preparation method of four oxidations, three tin/silver orthophosphate composite material photocatalyst, is following steps：
(1) by 2.5gSnCl2·2H2O is dissolved in 40mL deionized waters, and stirring 22min obtains stannous chloride solution, by lemon
Lemon acid trisodium is dissolved in stannous chloride solution, and stirring 20min obtains mixed solution, and the aqueous slkali that 40mL concentration is 0.15M is added
Enter in mixed solution, stir 20min；
(2) step (1) acquired solution is transferred in autoclave, in 155 DEG C of hydro-thermal reaction 20h, naturally cooled to
Reaction product is filtered, centrifuged, washes of absolute alcohol 4 times, in 68 DEG C of dry 8h, obtaining Sn by room temperature3O4Material；
(3) Sn for obtaining step (2)3O4Material, ultrasonic disperse are dissolved in 40mL in 80mL deionized waters, by silver salt
In ionized water, stirring 20min obtains silver salt solution under the conditions of room temperature is protected from light, by silver salt solution and Sn3O4Dispersion liquid mixes,
Stirring 40min obtains the first solution under the conditions of room temperature is protected from light；
(4) phosphate is dissolved in 40mL deionized waters, stirs 20min at room temperature and obtain phosphate solution, by phosphate
Solution is slowly added to dropwise in the first solution obtained by step (3), and the reaction was continued under the conditions of room temperature is protected from light after being added dropwise；
(5) by the filtering of step (4) reaction product, centrifuge, washes of absolute alcohol 5 times, in 75 DEG C of dry 10h to obtain the final product.
Aqueous slkali is potassium hydroxide solution in the step (1).
Silver salt is CH in the step (3)3COOAg, phosphate is Na in the step (4)3PO4, silver salt and phosphate
Middle Ag/PO4 3-Molar ratio be 3:1.
Ag/Sn in first solution in the step (3)3O4Molar ratio be 8:1.
The reaction time is 2.5h under the conditions of room temperature is protected from light in the step (4).
Embodiment 4
One kind four aoxidizes three tin/silver orthophosphate composite material photocatalyst, is flower-shaped Sn3O4Loaded Ag3PO4Nanosphere
Structure, by flower-shaped Sn3O4Growth in situ Ag on surface3PO4Nanosphere forms, the flower-shaped Sn3O4It is 50~100nm's by thickness
Thin slice is accumulated and forms flower-like structure, the Ag3PO4The grain size of nanosphere is 40~70nm.
A kind of preparation method of four oxidations, three tin/silver orthophosphate composite material photocatalyst, is following steps：
(1) by 3gSnCl2·2H2O is dissolved in 30mL deionized waters, and stirring 15min obtains stannous chloride solution, by lemon
Sour trisodium is dissolved in stannous chloride solution, and stirring 25min obtains mixed solution, the aqueous slkali that 40mL concentration is 0.2M is added in mixed
It closes in solution, stirs 15min；
(2) step (1) acquired solution is transferred in autoclave, in 185 DEG C of hydro-thermal reaction 20h, naturally cooled to
Reaction product is filtered, centrifuged, washes of absolute alcohol 3 times, in 75 DEG C of dry 8h, obtaining Sn by room temperature3O4Material；
(3) Sn for obtaining step (2)3O4Material, ultrasonic disperse are dissolved in 40mL in 85mL deionized waters, by silver salt
In ionized water, stirring 25min obtains silver salt solution under the conditions of room temperature is protected from light, by silver salt solution and Sn3O4Dispersion liquid mixes,
Stirring 45min obtains the first solution under the conditions of room temperature is protected from light；
(4) phosphate is dissolved in 20mL deionized waters, stirs 15min at room temperature and obtain phosphate solution, by phosphate
Solution is slowly added to dropwise in the first solution obtained by step (3), and the reaction was continued under the conditions of room temperature is protected from light after being added dropwise；
(5) by the filtering of step (4) reaction product, centrifuge, washes of absolute alcohol 5 times, in 75 DEG C of dry 10h to obtain the final product.
Aqueous slkali is sodium hydroxide solution in the step (1).
Silver salt is AgNO in the step (3)3, phosphate is Na in the step (4)2HPO4, in silver salt and phosphate
Ag/PO4 3-Molar ratio be 3:1.
Ag/Sn in first solution in the step (3)3O4Molar ratio be 10:1.
The reaction time is 2.5h under the conditions of room temperature is protected from light in the step (4).
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail in good embodiment, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and scope of technical solution of the present invention, should all be covered at this
Among the right of invention.
Claims (6)
1. one kind four aoxidizes three tin/silver orthophosphate composite material photocatalyst, which is characterized in that is flower-shaped Sn3O4Loaded Ag3PO4It receives
The structure of rice ball, by flower-shaped Sn3O4Growth in situ Ag on surface3PO4Nanosphere forms, the flower-shaped Sn3O4By thickness for 50~
The thin slice of 100nm is accumulated and forms flower-like structure, the Ag3PO4The grain size of nanosphere is 40~70nm.
2. a kind of preparation method of four oxidations, three tin/silver orthophosphate composite material photocatalyst as described in claim 1, feature
It is, is following steps：
(1) by 1~5gSnCl2·2H2O is dissolved in 20~60mL deionized waters, and 10~30min of stirring obtains stannous chloride solution,
2~10g trisodium citrates are dissolved in stannous chloride solution, 10~30min of stirring obtains mixed solution, by 20~50mL concentration
It is added in for the aqueous slkali of 0.05~0.5M in mixed solution, stirs 10~30min；
(2) step (1) acquired solution is transferred in autoclave, it is naturally cold in 120~200 DEG C of hydro-thermal reactions 12~for 24 hours
But to room temperature, reaction product is filtered, is centrifuged, washes of absolute alcohol 3~5 times, in 60~80 DEG C of dry 6~12h, is obtained
Sn3O4Material；
(3) Sn for obtaining step (2)3O4Material, ultrasonic disperse is dissolved in 20 in 50~100mL deionized waters, by silver salt~
In 50mL deionized waters, 10~30min of stirring obtains silver salt solution under the conditions of room temperature is protected from light, by silver salt solution and Sn3O4It is scattered
Liquid mixes, and 30~60min is stirred under the conditions of room temperature is protected from light and obtains the first solution；
(4) 20~80g phosphate is dissolved in 10~50mL deionized waters, it is molten to obtain phosphate by 10~30min of stirring at room temperature
Phosphate solution is slowly added in the first solution obtained by step (3), after being added dropwise under the conditions of room temperature is protected from light by liquid dropwise
The reaction was continued；
(5) by the filtering of step (4) reaction product, centrifuge, washes of absolute alcohol 3~5 times, in 60~80 DEG C of dry 6~12h
To obtain the final product.
3. a kind of preparation method of four oxidations, three tin/silver orthophosphate composite material photocatalyst as claimed in claim 2, feature
It is, aqueous slkali is sodium hydroxide or potassium hydroxide solution in the step (1).
4. a kind of preparation method of four oxidations, three tin/silver orthophosphate composite material photocatalyst as claimed in claim 2, feature
It is, silver salt is AgNO in the step (3)3Or CH3COOAg, phosphate is Na in the step (4)3PO4Or Na2HPO4, silver
Ag/PO in salt and phosphate4 3-Molar ratio be 3:1.
5. a kind of preparation method of four oxidations, three tin/silver orthophosphate composite material photocatalyst as claimed in claim 2, feature
It is, Ag/Sn in the first solution in the step (3)3O4Molar ratio be 5:1~50:1.
6. a kind of preparation method of four oxidations, three tin/silver orthophosphate composite material photocatalyst as claimed in claim 2, feature
It is, the reaction time is 2~3h under the conditions of room temperature is protected from light in the step (4).
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