CN108579775A - A kind of silver orthophosphate/silver/titanium dioxide nano flower composite material and the preparation method and application thereof - Google Patents
A kind of silver orthophosphate/silver/titanium dioxide nano flower composite material and the preparation method and application thereof Download PDFInfo
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- CN108579775A CN108579775A CN201810463799.6A CN201810463799A CN108579775A CN 108579775 A CN108579775 A CN 108579775A CN 201810463799 A CN201810463799 A CN 201810463799A CN 108579775 A CN108579775 A CN 108579775A
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- silver
- titanium dioxide
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- titanium oxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000002057 nanoflower Substances 0.000 title claims abstract description 64
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 33
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 25
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 71
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004332 silver Substances 0.000 claims abstract description 36
- 229910052709 silver Inorganic materials 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- NDYNABNWLRVCDO-UHFFFAOYSA-N phosphoric acid silver Chemical compound [Ag].P(O)(O)(O)=O NDYNABNWLRVCDO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 10
- 125000000468 ketone group Chemical group 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000002055 nanoplate Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005234 chemical deposition Methods 0.000 claims description 5
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 238000001338 self-assembly Methods 0.000 abstract description 5
- 239000002135 nanosheet Substances 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 229960005196 titanium dioxide Drugs 0.000 description 70
- 235000010215 titanium dioxide Nutrition 0.000 description 43
- 230000001699 photocatalysis Effects 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 229910003087 TiOx Inorganic materials 0.000 description 4
- AMHXQVUODFNFGR-UHFFFAOYSA-K [Ag+3].[O-]P([O-])([O-])=O Chemical group [Ag+3].[O-]P([O-])([O-])=O AMHXQVUODFNFGR-UHFFFAOYSA-K 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses methods prepared by a kind of silver orthophosphate/silver/titanium dioxide nano flower composite material.Silver orthophosphate prepared by the present invention/silver/titanium dioxide nano flower composite material is combined a kind of Z Scheme heterojunction structures by ultra micro phosphoric acid silver nano-grain, silver nano-grain and three component of titanium oxide nanoflower.Titanium oxide nanoflower is self-assembly of by ultra-thin titanium dioxide nanosheet, is provided bigger serface and is rich in a large amount of Lacking oxygens.A small amount of silver ion is restored by titanium oxide nanoflower Lacking oxygen, and homogeneous reduction is deposited on its surface, has close interfacial contact between the two, then, using simple chemical coprecipitation, one layer of phosphoric acid silver nano-grain is coated on the surface of silver nano-grain.Silver orthophosphate provided by the invention/silver/titanium dioxide nano flower composite material is a kind of efficient, stable photoelectric conversion material, and using simple chemical preparation process, preparation process is simple, easy control of reaction conditions, is suitable for extensive preparation and industrialized production.
Description
Technical field
The present invention relates to a kind of silver orthophosphate/silver/titanium dioxide nano flower composite materials and the preparation method and application thereof, belong to
Nano material and photocatalysis technology field.
Background technology
Energy problem is that the mankind depend on for existence and development a kind of important resource.Solar energy, which has, to be cleaned, is cheap, renewable
The advantages that, thus efficiently and rapidly using, conversion and storage solar energy be people make great efforts target.Photocatalitic Technique of Semiconductor is just
It is with the chemical conversion of solar energy and to be stored as core, absorbs solar energy by using semi-conducting material, and solar energy is converted
It is considered as current one of the main means for solving mankind's energy crisis at other pollution-free and reproducible new energy.
Silver orthophosphate is widely used in water process, photodissociation as a kind of novel visible light-responded conductor photocatalysis material
The fields such as water, exhaust-gas treatment and antibacterial.It has many advantages, such as that photocatalytic activity is high, pattern is adjustable, the quantum of photochemical catalyzing
Efficiency is up to 90%, and analysis oxygen rate is 3 times and 8 times of pucherite and tungsten oxide respectively so that it has important research significance
And prospect of the application.But silver ion is easy to be reduced into silver-colored simple substance by itself light activated light induced electron, and silver orthophosphate is caused to lose
Therefore activity greatly limits its photocatalytic activity.
In the past few decades, titanium dioxide by most widely used in photocatalysis field, still, due to titanium dioxide spectrum ring
Narrow range is answered, the problems such as light utilization efficiency is low and its photo-generated carrier is compound serious, limits its large-scale industrialization.Currently,
A large amount of researcher improves the photocatalysis performance of titanium dioxide by various strategies, main method have Morphological control,
Noble metal loading and semiconductors coupling.Wherein, the nano material of the titanium dioxide classification nanometer flower structure of suitable dimension is prepared
It is considered as the new strategy for improving optically catalytic TiO 2 performance, since it shows unique physicochemical properties：It is lower
Light reflectivity preferably improves physics light absorption, possesses the advantages that providing more multiple reaction site and active site.It can be in certain journey
The light abstraction width of titanium dioxide has been widened on degree and improves the service life of its photoproduction current-carrying.This makes its answering in photocatalysis field
With being concerned.In addition, titanium dioxide is considered as most effective raising titanium dioxide with other semiconductors couplings structure heterojunction structure
The mode of titanium photocatalytic activity.For example it can be built therebetween in titanium dioxide surface deposition silver orthophosphate structure heterojunction structure
Photo-generated carrier split tunnel effectively improves its photocatalytic activity
Using the Lacking oxygen defect reduction silver ion on titanium oxide nanoflower surface dioxy is deposited on as silver nano-grain
Change titanium nano flower surface, then, is deposited on the silver nano-grain surface on titanium oxide nanoflower surface by chemical coprecipitation
One layer of silver orthophosphate.The special Z-Scheme structures of nucleocapsid are built, silver nano-grain transmits body as electron hole, makes two
TiOx nano spend in electronics and silver orthophosphate in hole occur compound and bury in oblivion, leave the photoproduction of superpower redox ability
Electrons and holes, the method is easy to operate, nontoxic, efficient and with can large area manufacturing feasibility.
Invention content
Purpose of the present invention is in view of the above-mentioned problems, providing a kind of system of silver orthophosphate/silver/titanium dioxide nano flower composite material
Preparation Method solves titanium-dioxide photo incomplete absorption in the prior art, and light utilization efficiency is low, silver orthophosphate stability difference and photocatalysis
The problems such as agent recycling is difficult.
The present invention adopts the following technical scheme that；A kind of ultra micro nano silver/silver/titanium dioxide nano flower composite material
Preparation method, described steps are as follows：
Step 1：First isopropanol is added in diethylenetriamine, is stirred evenly, two (levulinic ketone group) metatitanic acids are added
The volume ratio of diisopropyl ester, isopropanol, diethylenetriamine and two (levulinic ketone group) metatitanic acid diisopropyl esters is 1260~2520:1
~10:45~360, it stirs evenly, pours into reaction kettle, under the conditions of 200~220 DEG C, solvent heat treatment 24~36 hours is washed
It washs, it is dry, nano material will be obtained, annealing temperature is warming up to 1~10 DEG C/min, annealing temperature is 450 DEG C, annealing time 2
Hour, obtain the oxygen-enriched vacancy titanium oxide nanoflower material of presoma.
Step 2：Presoma titanium oxide nanoflower material is dispersed with stirring in 30mL ethyl alcohol；Weigh 200~400mg nitre
It is 1~2% that sour silver, which is dissolved in mass fraction, in the ammonium hydroxide that volume is 10ml in solution, obtains silver ammino solution；Silver ammino solution is added dropwise
Into titanium dioxide alcohol dispersion liquid；It is 10mL by volume under stirring, 0.2~0.4mol/L biphosphates receive solution
It is added dropwise in mixed solution, silver nitrate is 1 with titanium oxide nanoflower forerunner's body mass ratio:2~4, chemical deposition silver orthophosphate
Grain is stood, eccentric cleaning, is placed in baking oven 60 DEG C, and drying 12 hours obtains silver orthophosphate/titanium oxide nanoflower composite material.
Further, in step 1 reaction temperature be 200 DEG C, the reaction time be 24 hours, isopropanol, diethylenetriamine and
The volume ratio of two (levulinic ketone group) metatitanic acid diisopropyl esters is 1260:1:45.
Further, silver nitrate 200mg in step 2, ammonium hydroxide mass fraction 1%, phosphate dihydrogen sodium concentration 0.2mol/l, nitre
Sour silver is 1 with titanium oxide nanoflower ratio:2.
A kind of ultra micro nano silver/silver/titanium dioxide nano flower composite material, which is characterized in that the titanium dioxide
Nano flower is made of the titanium dioxide nanoplate of Anatase, 2~9nm of titanium dioxide nanoplate thickness；Phosphoric acid silver nano-grain
Silver nano-grain is coated, size is formed in the nano particle of 1~4nm, is carried on titanium dioxide nanoplate surface, and formed heterogeneous
Knot.
The silver orthophosphate/application of the silver/titanium dioxide nano flower composite material as photochemical catalyst：Hydrogen production by water decomposition, point
Xie Shui oxygen, degradation of contaminant, biological antibiotic, other related fields such as photoelectric decomposition water and organic synthesis.
The beneficial effects of the present invention are：A kind of simple method of present invention offer prepares ultra micro nano silver/silver/bis-
TiOx nano floral material.First, oxygen-enriched vacancy titanium oxide nanoflower is prepared by simple step solvent-thermal method and is used as carrier,
Then the Lacking oxygen being rich in by titanium oxide nanoflower restores a part of silver ion and is deposited on dioxy as silver nano-grain
Change the surface of titanium nano flower, then, one layer of silver orthophosphate is deposited on the surface of silver nano-grain by chemical coprecipitation.The dioxy
Change titanium nano flower carrier to be self-assembly of by anatase phase titanium dioxide nanometer sheet, there is three-dimensional hierarchical structure, two can be expanded
TiOx nano spends the absorption region of visible light, increases the Multiple Scattering performance of light, and fast transfer photoelectron and increase are more
Adsorption site and reaction site.Still further aspect is deposited on the silver nano-grain on titanium oxide nanoflower surface as titanium dioxide
The electron-hole recombinations medium of titanium nano flower and silver orthophosphate makes the electronics in the hole and silver orthophosphate in titanium oxide nanoflower send out
Life is compound and buries in oblivion, and leaves light induced electron and the hole of the superpower redox ability of the two.Silver orthophosphate/silver/titanium dioxide ternary
A kind of Z-Scheme heterojunction structures are compounded to form, the separation of its photo-generated carrier is promoted, are efficiently joined using light induced electron and hole
With redox reaction, the photocatalysis performance of composite material is improved.In addition, this material preparation method is simple, size is easy to control and
Conducive to industrialized production, therefore, the present invention greatly reduces ultra micro nano silver/silver/titanium dioxide nano flower composite material
Production cost and significantly improve its photocatalysis performance, have great application prospect.
Description of the drawings
Fig. 1 shows the X-ray diffractograms (XRD) of silver orthophosphate made from example 1/silver/titanium dioxide nano flower composite material.
The Ag swarming collection of illustrative plates of the XPS of composite material obtained by Fig. 2 embodiments 1；
Fig. 3 indicates the scanning electron microscope diagram of silver orthophosphate/silver/titanium dioxide nano flower composite material made from example 1
(SEM)。
Fig. 4,5 indicate that silver orthophosphate/silver/titanium dioxide nano flower composite material is under different amplification made from example 1
Transmission electron microscope figure (TEM).
Fig. 6 is photodissociation when prepared silver orthophosphate/silver/titanium dioxide nano flower composite material is as photochemical catalyst in example 1
Aquatic products oxygen curve graph.
Specific implementation mode：
With reference to embodiment, the invention will be further described.Following embodiment is used for illustrating the present invention, without
It is to limit the invention, in the protection domain of spirit and claims of the present invention, any is repaiied to what the present invention made
Change and change, both falls within protection scope of the present invention.
Embodiment 1：
Step 1：Diethylenetriamine (EDTA) 0.025mL is added in 31.5mL isopropanols, stirs 10min.Again toward solution
In add two (levulinic ketone group) metatitanic acid diisopropyl ester 1.125mL.Continue to stir 10min.Gained mixed solution is poured into instead
It answers in kettle, the solvent heat treatment 24 hours under the conditions of 200 DEG C.After reaction by sediment deionized water and absolute ethyl alcohol point
It does not wash three times, is placed in 60 DEG C of baking ovens, it is 24 hours dry, finally reactant is placed in Muffle furnace, 1 DEG C of heating rate/
Min, 450 DEG C of heat treatment temperature anneal 2 hours, obtain presoma titanium oxide nanoflower material.
Step 2：Step 2：100mg presoma titanium oxide nanoflower materials are dispersed with stirring in 30mL ethyl alcohol, appropriateness
Ultrasound is uniformly dispersed；It is 1% to weigh 200mg silver nitrates to be dissolved in mass fraction, in the ammonium hydroxide that volume is 10ml in solution, is obtained
To silver ammino solution；Fresh silver ammino solution is added dropwise in titanium dioxide alcohol dispersion liquid, until silver ion absorption is complete；It is stirring
It is 10mL by volume under state, 0.2mol/L biphosphates are received solution and are added dropwise in mixed solution, and control drop speed 1 drips/3 seconds left sides
The right side, chemical deposition phosphoric acid Argent grain are stood, and eccentric cleaning is placed in baking oven 60 DEG C, 12 hours dry, obtain silver orthophosphate/silver/
Titanium oxide nanoflower composite material.
The XRD diagram of composite material obtained by Fig. 1 embodiments 1, it is seen that the peak of two object phases of silver orthophosphate and titanium dioxide, two
The XRD diffraction patterns and standard Ag of person3PO4With anatase TiO2Characteristic peak be consistent, not observe elemental silver characteristic peak, can
The reason of energy is that Ag contents are very little.
The Ag swarming collection of illustrative plates of the XPS of composite material obtained by Fig. 2 embodiments 1, it is seen that have in prepared composite material
The presence of a small amount of silver simple substance, it is the Lacking oxygen reduction being rich in by titanium oxide nanoflower by a small amount of silver to exist.
Fig. 3 is the SEM figures of composite material obtained by embodiment 1, it is seen that the size of titanium oxide nanoflower 500~
1000nm, does not observe the presence of silver orthophosphate and silver nano-grain, reason may be silver orthophosphate and silver nano-grain size too
It is small.
Figure 4 and 5 are that the transmitted electron of ultra micro silver orthophosphate/silver/titanium dioxide nano flower composite material made from embodiment 1 is aobvious
Micro mirror figure (TEM), it can be seen from the figure that phosphoric acid silver nano-grain coated with silver nano particle, forms size receiving in 2~4nm
Rice grain is carried on titanium dioxide nanoplate surface, and forms hetero-junctions.
Take silver orthophosphate/silver/titanium dioxide nano flower composite material ultrasonic disperse prepared by 50mg the present embodiment in 100mL
In deionized water, into dispersion liquid, addition 200mg silver nitrates are as electron capture agent, the dispersion that ultrasonic disperse is obtained after uniform
Liquid is transferred in photo catalysis reactor, is placed under dark condition and is stood 30 minutes, whole device is vacuumized.And it is placed in illumination
Under, it is primary every sampling in 30 minutes, the amount of oxygen is produced with gas chromatographic detection, to draw out ultra micro nano silver/silver/bis-
The curve graph of TiOx nano flower composite material photocatalysis Decomposition aquatic products oxygen under light illumination.Fig. 6 is that the light that test obtains is urged
Change the curve graph for decomposing aquatic products oxygen, as can be seen from the figure composite material exhibits go out decomposes aqueous energy well.
Embodiment 2
Step 1：Diethylenetriamine (EDTA) 0.025mL is added in 31.5mL isopropanols, stirs 10min.Again toward solution
In add two (levulinic ketone group) metatitanic acid diisopropyl ester 1.125mL.Continue to stir 10min.Gained mixed solution is poured into instead
It answers in kettle, the solvent heat treatment 24 hours under the conditions of 200 DEG C.After reaction by sediment deionized water and absolute ethyl alcohol point
It does not wash three times, is placed in 60 DEG C of baking ovens, it is 24 hours dry, finally reactant is placed in Muffle furnace, 1 DEG C of heating rate/
Min, 450 DEG C of heat treatment temperature anneal 2 hours, obtain presoma titanium oxide nanoflower material.
Step 2：Step 2：100mg presoma titanium oxide nanoflower materials are dispersed with stirring in 30mL ethyl alcohol, appropriateness
Ultrasound is uniformly dispersed；It is 2% to weigh 400mg silver nitrates to be dissolved in mass fraction, in the ammonium hydroxide that volume is 10ml in solution, is obtained
To silver ammino solution；Fresh silver ammino solution is added dropwise in titanium dioxide alcohol dispersion liquid, until silver ion absorption is complete；It is stirring
It is 10mL by volume under state, 0.4mol/L biphosphates are received solution and are added dropwise in mixed solution, and control drop speed 1 drips/3 seconds left sides
The right side, chemical deposition phosphoric acid Argent grain are stood, and eccentric cleaning is placed in baking oven 60 DEG C, 12 hours dry, obtain silver orthophosphate/silver/
Titanium oxide nanoflower composite material.
Through characterization, the titanium oxide nanoflower material, size is 500~1000nm, by ultra-thin titanium dioxide nanosheet
It is self-assembly of, nanometer sheet thickness is 2~9nm.Phosphoric acid silver nano-grain coated with silver nano particle forms size 1~3nm's
Nano particle is carried on titanium dioxide nanoplate surface, and forms hetero-junctions.Material XRD diffraction patterns and standard Anatase
TiO2And the characteristic peak of standard phosphate silver is consistent.
According to the method photocatalysis Decomposition aquatic products oxygen of embodiment 1, show to decompose aqueous energy well.
Embodiment 3
Step 1：Diethylenetriamine (EDTA) 0.125mL is added in 31.5mL isopropanols, stirs 10min.Again toward solution
In add two (levulinic ketone group) metatitanic acid diisopropyl ester 4.5mL.Continue to stir 10min.Gained mixed solution is poured into reaction
In kettle, the solvent heat treatment 24 hours under the conditions of 220 DEG C.Sediment deionized water and absolute ethyl alcohol are distinguished after reaction
Washing three times, is placed in 60 DEG C of baking ovens, 24 hours dry, finally reactant is placed in Muffle furnace, 10 DEG C/min of heating rate,
450 DEG C of heat treatment temperature anneals 2 hours, obtains presoma titanium oxide nanoflower material.
Step 2：100mg presoma titanium oxide nanoflower materials are dispersed with stirring in 30mL ethyl alcohol, appropriateness ultrasound will
It is uniformly dispersed；It is 1% to weigh 200mg silver nitrates to be dissolved in mass fraction, in the ammonium hydroxide that volume is 10ml in solution, obtains silver-colored ammonia
Solution；Fresh silver ammino solution is added dropwise in titanium dioxide alcohol dispersion liquid, until silver ion absorption is complete；In stirring
Under, it is 10mL by volume, 0.2mol/L biphosphates are received solution and are added dropwise in mixed solution, and 1 drop/3 seconds or so of control drop speed is changed
Deposition phosphoric acid Argent grain is learned, is stood, eccentric cleaning, is placed in baking oven 60 DEG C, drying 12 hours obtains silver orthophosphate/silver/titanium dioxide
Titanium nano flower composite material.
Through characterization, the titanium oxide nanoflower material, size is 500~1000nm, by ultra-thin titanium dioxide nanosheet
It is self-assembly of, nanometer sheet thickness is 2~9nm.Small size phosphoric acid silver nano-grain is dispersed in titanium oxide nanoflower piece
On, heterojunction structure is formed, the particle size of ultra micro phosphoric acid Argent grain is 1~4nm, material XRD diffraction patterns and standard rutile titania
Mine phase TiO2And the characteristic peak of standard phosphate silver is consistent.
Embodiment 4
Step 1：Diethylenetriamine (EDTA) 0.125mL is added in 31.5mL isopropanols, stirs 10min.Again toward solution
In add two (levulinic ketone group) metatitanic acid diisopropyl ester 4.5mL.Continue to stir 10min.Gained mixed solution is poured into reaction
In kettle, the solvent heat treatment 24 hours under the conditions of 220 DEG C.Sediment deionized water and absolute ethyl alcohol are distinguished after reaction
Washing three times, is placed in 60 DEG C of baking ovens, 24 hours dry, finally reactant is placed in Muffle furnace, 10 DEG C/min of heating rate,
450 DEG C of heat treatment temperature anneals 2 hours, obtains presoma titanium oxide nanoflower material.
Step 2：Step 2：100mg presoma titanium oxide nanoflower materials are dispersed with stirring in 30mL ethyl alcohol, appropriateness
Ultrasound is uniformly dispersed；It is 2% to weigh 400mg silver nitrates to be dissolved in mass fraction, in the ammonium hydroxide that volume is 10ml in solution, is obtained
To silver ammino solution；Fresh silver ammino solution is added dropwise in titanium dioxide alcohol dispersion liquid, until silver ion absorption is complete；It is stirring
It is 10mL by volume under state, 0.4mol/L biphosphates are received solution and are added dropwise in mixed solution, and control drop speed 1 drips/3 seconds left sides
The right side, chemical deposition phosphoric acid Argent grain are stood, and eccentric cleaning is placed in baking oven 60 DEG C, 12 hours dry, obtain silver orthophosphate/silver/
Titanium oxide nanoflower composite material.
Through characterization, the titanium oxide nanoflower material, size is 500~1000nm, by ultra-thin titanium dioxide nanosheet
It is self-assembly of, nanometer sheet thickness is 2~9nm.Phosphoric acid silver nano-grain coated with silver nano particle forms size 1~4nm's
Nano particle is carried on titanium dioxide nanoplate surface, and forms hetero-junctions.Material XRD diffraction patterns and standard Anatase
TiO2And the characteristic peak of standard phosphate silver is consistent.
According to the method photocatalysis Decomposition aquatic products oxygen of embodiment 1, show to decompose aqueous energy well.
Claims (5)
1. a kind of preparation method of ultra micro nano silver/silver/titanium dioxide nano flower composite material, which is characterized in that described
Steps are as follows：
Step 1：First isopropanol is added in diethylenetriamine, is stirred evenly, it is different to add two (levulinic ketone group) metatitanic acids two
The volume ratio of propyl ester, isopropanol, diethylenetriamine and two (levulinic ketone group) metatitanic acid diisopropyl esters is 1260~2520:1~10:
45~360, it stirs evenly, pours into reaction kettle, under the conditions of 200~220 DEG C, solvent heat treatment 24~36 hours is washed, and is done
It is dry, nano material will be obtained, annealing temperature is warming up to 1~10 DEG C/min, annealing temperature is 450 DEG C, and annealing time is 2 hours,
Obtain the oxygen-enriched vacancy titanium oxide nanoflower material of presoma.
Step 2：Presoma titanium oxide nanoflower material is dispersed with stirring in 30mL ethyl alcohol；Weigh 200~400mg silver nitrates
It is 1~2% to be dissolved in mass fraction, in the ammonium hydroxide that volume is 10ml in solution, obtains silver ammino solution；Silver ammino solution is added dropwise to two
In titanium oxide alcohol dispersion liquid；Under stirring, by volume be 10mL, 0.2~0.4mol/L biphosphates receive solution dropwise addition
Enter in mixed solution, silver nitrate is 1 with titanium oxide nanoflower forerunner's body mass ratio:2~4, chemical deposition phosphoric acid Argent grain is quiet
It sets, eccentric cleaning, is placed in baking oven 60 DEG C, drying 12 hours obtains silver orthophosphate/titanium oxide nanoflower composite material.
2. the method as described in claim 1, which is characterized in that reaction temperature is 200 DEG C in step 1, and the reaction time is 24 small
When, the volume ratio of isopropanol, diethylenetriamine and two (levulinic ketone group) metatitanic acid diisopropyl esters is 1260:1:45.
3. the method as described in claim 1, which is characterized in that silver nitrate 200mg in step 2, ammonium hydroxide mass fraction 1%, phosphorus
Acid dihydride na concn 0.2mol/l, silver nitrate are 1 with titanium oxide nanoflower ratio:2.
4. ultra micro nano silver/silver/titanium dioxide nano flower composite material that method as described in claim 1 is prepared,
It is characterized in that, the titanium oxide nanoflower is made of the titanium dioxide nanoplate of Anatase, titanium dioxide nanoplate is thick
Spend 2~9nm；Phosphoric acid silver nano-grain coated with silver nano particle forms size in the nano particle of 1~4nm, is carried on titanium dioxide
Titanium nanometer sheet surface, and form hetero-junctions.
5. the ultra micro nano silver that method as described in claim 1 is prepared/silver/titanium dioxide nano flower composite material is made
For the application of photochemical catalyst, which is characterized in that including hydrogen production by water decomposition, decompose water oxygen, degradation of contaminant, biological antibiotic, light
Electrolysis water, organic synthesis etc..
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| CN112774695A (en) * | 2021-01-28 | 2021-05-11 | 南京大学 | Direct Z-type heterojunction photocatalyst capable of being used for decomposing water and preparation method thereof |
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