CN108722499A - A kind of preparation method of titanate ink and the method for the porous titanate artificial light zoarium system of printing - Google Patents
A kind of preparation method of titanate ink and the method for the porous titanate artificial light zoarium system of printing Download PDFInfo
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- CN108722499A CN108722499A CN201810468916.8A CN201810468916A CN108722499A CN 108722499 A CN108722499 A CN 108722499A CN 201810468916 A CN201810468916 A CN 201810468916A CN 108722499 A CN108722499 A CN 108722499A
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- titanate
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000007639 printing Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010146 3D printing Methods 0.000 claims abstract description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- -1 salt compounds Chemical class 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 77
- 239000004408 titanium dioxide Substances 0.000 claims description 33
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 15
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 12
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 229920002415 Pluronic P-123 Polymers 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 241001274660 Modulus Species 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 229940099259 vaseline Drugs 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229920001992 poloxamer 407 Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 229910052712 strontium Inorganic materials 0.000 abstract description 5
- 239000010936 titanium Substances 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 238000000265 homogenisation Methods 0.000 abstract description 2
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000036314 physical performance Effects 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical class [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011325 microbead Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical class [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 206010068516 Encapsulation reaction Diseases 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002334 glycols Chemical class 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical class [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method preparing titanate ink and the porous titanate artificial light zoarium system of printing, main contents include the following steps：The salt compounds of A are completely dissolved in organic solvent, the metal A is selected from metal Sr, Ca, one kind in Pb, then Titanium alkoxides, acetylacetone,2,4-pentanedione, surfactant, nanometer silicon dioxide particle, polyvinylpyrrolidone and concentrated ammonia liquor is added, it is titanate ink that concentration homogenisation liquid is obtained after solvent is volatilized, which is transferred to 3D printing barrel and is installed in 3D printing equipment, writes G-code codes setting printing path and prints and constructs three-dimensional structure；Three-dimensional structure obtains three-dimensional titanate artificial light condensation material by roasting and with thermokalite potassium hydroxide selective etch.The artificial photosystem of three-dimensional titanate prepared by the present invention can significantly improve the CO of material2Photo-reduction generates nytron physical performance, and its structure-controllable.
Description
Technical field
The invention belongs to material preparation and photocatalysis technology field, more particularly to the preparation method of a kind of titanate ink and
The method for printing porous titanate artificial light zoarium system.
Background technology
Energy problem and environmental problem are world today's important problems, and clean energy resource, degradation are generated using photocatalysis technology
Pollutant will be helpful to alleviate energy and environmental problem.It is proven to have photodissociation aquatic products hydrogen from titanium dioxide the 1970s
Since performance, catalysis material has obtained extensive research and development.The artificial photosystem water common by consuming nature
And CO2The clean energy resourcies such as hydrocarbon, hydrogen are generated, similar nature photosynthesis is a kind of novel effective energy technology.
Titanium dioxide is the most commonly used catalysis material of research, other titanates with perovskite structure based on titanium dioxide
Also it is widely studied and applied, such as strontium titanates, calcium titanate, lead titanates etc., these titanates are all proved can be made into artificial photosynthetic
System.
Porous photocatalytic material is always photocatalysis field research hotspot, and introducing is porous can effectively to promote material specific surface area
To increase reactivity site significantly, this captures reaction process light, matter transmission has very great help, and porous photocatalytic material is past
It is more efficient toward catalysis material more non-porous than correspondence.Around porous titanate photocatalytic system, there are many document reports, such as China
Patent CN104383906A, entitled " a kind of preparation method of porous strontium titanate visible light catalyst ", the technical characterstic of the patent exists
In providing a kind of method for being prepared using sol-gel method and synthesizing porous strontium titanate visible light catalyst, with the poly- second of different molecular weight
Glycol series of surfactants synthesizes the porous strontium titanate material with high porosity and high-specific surface area as pore former, but
It is that the technology is single using polyethylene glycol as pore former, the porous size of formation receives limitation, only forms the single POROUS TITANIUM in aperture
Sour strontium catalysis material；Such as Chinese patent CN105000594A, entitled " a kind of graduation porous titania microbead and its system
Preparation Method ", the technical characterstic of the patent are the provision of a kind of graduation porous titania microbead and preparation method thereof and answer
With, the shortcomings of solving the preparation method complexity of existing graduation poriferous titanium dioxide material and need subsequent processing, and
This material is constructed for the first time and is detected applied to acetone gas as gas sensor, which proposes simple and be not required to subsequently locate
The graduation poriferous titanium dioxide material preparation method of reason, but it is powder that the technology, which finally obtains graduation poriferous titanium dioxide,
There is the shortcomings that not easily collecting and recycling in system, this is also other powder photocatalytic systems in practical photocatalytic applications
The defect of generally existing；For another example Chinese patent CN104477983A, entitled " the preparation side of layer stephanoporate titanium dioxide block
The technical characterstic of method ", the patent is the provision of a kind of preparation method of layer stephanoporate titanium dioxide block, this method technique letter
Single, at low cost, mild condition, prepared titanium dioxide block has good mechanical strength, is formed by after subsequent processing
Gap is evenly distributed；The patent system can effectively avoid powder systems not easily collecting and recycling for light extraction catalytic mass material
Defect, but titanium dioxide block prepared by the technology is simple porous bulk, can not be formed with the frame of specific structure, no
Energy design structure, is difficult to that luminous energy conversion devices are made in practice.
Invention content
The present invention provides the preparation method of titanate ink and the method for the porous titanate artificial light zoarium system of printing, energy gram
Take current powder photocatalytic system it is inefficient, not easily collecting recycling deficiency, utilize 3D printing technique realize three dimension high efficiency light
The structuring of catalyst system and catalyzing is constructed, and the porous titanate artificial light zoarium system of preparation has high-ratio surface and gas efficiency of transmission,
And different structure can be designed according to actual demand and be applied to distinct device.The side of this porous titanate artificial light zoarium system of printing
For photocatalysis technology, further application provides more possibility to method.
Technical scheme is as follows：
A kind of preparation method of titanate ink, includes the following steps：
S1：The salt compounds of metal A are dissolved in organic solvent B, organic solution is obtained；The metal A is selected from gold
Belong to Sr, one kind in Ca, Pb, the one kind of organic solvent in ethyl alcohol, isopropanol, n-butanol；
S2：Tetraisopropyl titanate and acetylacetone,2,4-pentanedione are added into the organic solvent that step S1 is obtained, is obtained after stirring
Mixed solution I；
S3：The surfactant C into the mixed solution I that step S2 is obtained is uniformly mixed, obtains mixed solution II；
S4：Nanometer silicon dioxide particle is added into the mixed solution II, is cleaned by ultrasonic, obtains mixed solution III；It is super
The sound time to be uniformly dispersed as foundation, preferably 30-240 minutes；
S5：Polyvinylpyrrolidone (PVP) and concentrated ammonia liquor are added into the mixed solution III, obtains mixed solution IV；
Wherein, polyvinylpyrrolidone, which plays static stabilization, can weaken the volume change that printer model is burnt processing generation, and concentrated ammonia liquor rises
It is acted on to hydrolysis rate is adjusted；
S6：The concentration of IV solvent flashing of the mixed solution is obtained into the titanate ink.The concentration time is by heating temperature
Degree and original organic solvent amount determine that organic solvent is more, and heating temperature is lower, and concentration time is longer, but are no more than 12 hours.
Preferably, surfactant C described in the step S3 is selected from triblock copolymer-pluronic F127
(F127), triblock copolymer-pluronic P123 (P123), lauryl sodium sulfate (SDS), cetyl trimethyl bromination
Ammonium (CTAB), one kind in dodecyl benzene sulfonic acid (DBSA).
Preferably, the molar ratio of the tetraisopropyl titanate and the metal A and gained titanate corresponding element atomic ratio
Unanimously, the preferred 10-80% of mass ratio of the salt compounds and organic solvent of the metal A；Tetraisopropyl titanate and levulinic
The molar ratio of ketone is 50%；The mass ratio of the surfactant C and tetraisopropyl titanate is 5-25%；Nano silicon dioxide
The mass ratio of grain and tetraisopropyl titanate is preferably 1-10%；The quality of the polyvinylpyrrolidone and tetraisopropyl titanate
Than preferred 4-6%；The preferred 1-2% of the mass ratio of the concentrated ammonia liquor and tetraisopropyl titanate.Wherein, surfactant C and nanometer
The change of silica volume changes the specific surface area for leading to artificial photosystem and meso pore characteristics, amount more at most specific surface
Product is bigger, and the nano silicon dioxide diameter the big, and it is bigger to form mesopore size.
Preferably, nanometer silicon dioxide particle size described in the step S4 is 15nm, 30nm or 50nm.It selects different
Diameter nanometer silicon dioxide particle, then nanometer silicon dioxide particle is different with the preferred section of mass ratio of tetraisopropyl titanate：Its
In a diameter of 15nm, the preferred 1-10% of mass ratio；A diameter of 30nm, the preferred 1-6% of mass ratio；A diameter of 50nm, mass ratio are excellent
Select 1-3%.
Preferably, the addition of metal A described in the step S1 is 0, and the titanate ink that step S6 is obtained is
Titanium dioxide ink.
Preferably, when the volume of the concentrated liquid reaches the 10-20% of former mixed liquor volume in the step S6, it can be used as metatitanic acid
Salt ink uses.
Preferably, the titanate ink is in semisolid, and storage modulu and loss modulus are 104The Pa orders of magnitude, and
Storage modulu is more than loss modulus.
The present invention also provides a kind of methods of the porous titanate artificial light zoarium system of printing, include the following steps：
T1：Titanate ink is transferred to 30mL polypropylene 3D printing barrels；Be installed in 3D printing equipment and and air pressure
Transmitting device connects；Boron glass syringe needle is connected on 3D printing barrel；
The 3D printing equipment is the Einstar-5 type 3D printings system of Hangzhou Xianlin Three-dimensional Science Co., Ltd's production
System；The 3D printing syringe needle is from drawing boron glass syringe needle, preferably 5 μm, 10 μm, 30 μm of needle tip diameter；
T2：Printing path is set by the titanate ink printed at three by writing G-code code drawing three-dimensional models
Structure is tieed up, print procedure carries out on plane vaseline matrix, and temperature is 20-30 DEG C, humidity 30-50%, pressure 0.1-
0.3mPa, syringe needle movement speed are 0.5-3mms-1；
T3：The three-dimensional structure that printing is constructed is transferred to air dry oven, 20-40 DEG C keeps the temperature 12-24 hours；
T4：Titanate three-dimensional structure is roasted 4-6 hours in 500-650 DEG C；
T5：Three-dimensional structure after roasting is immersed into 6mol/L potassium hydroxide solutions and is placed in water heating kettle, 160-200 DEG C of heat preservation
48-72 hours, washing and drying was up to the artificial photosystem of titanate with three-dimensional structure.
In above-mentioned steps T2, the threedimensional model is determined according to specific requirement, and successively arrangement bavin pile model, honeycomb can be selected
Model etc.；The preferred section of pressure of the preferred 0.1-0.3mPa of force of impression, variable-diameter pinhead are different, wherein 5 μm of syringe needles
It is preferred that 0.25-0.3mPa, 10 μm of syringe needles preferred 0.15-0.25mPa, 30 μm of preferred 0.1-0.15mPa of syringe needle；The print speed
It is preferred that 0.5-3mms-1, the preferred section of pressure of variable-diameter pinhead is different, wherein 5 μm of preferred 0.5-1mms of syringe needle-1, 10
μm preferred 0.5-1.5mms of syringe needle-1, 30 μm of preferred 0.5-3mms of syringe needle-1。
Preferably, the titanate ink in the step T1 is selected from obtained by the preparation method of above-mentioned titanate ink
Titanate ink.
Preferably, the artificial photosystem specific surface area of the titanate is 150-270m2/ g is classified mesoporous containing 2-25nm.
The present invention is based on following principles：Have using porous titanate artificial light zoarium system prepared by three-dimensional direct writing technology macro
Three-dimensional structure is seen, while there is classification meso-hole structure (aperture section 2-25nm) and high specific surface area (up to 270m2g-1) can
Light capture is effectively facilitated, and further lift gas efficiency of transmission, reaction gas and generation gas quickly can spread acceleration reaction
Further carry out.
Compared with prior art, beneficial effects of the present invention are as follows：
(1) present invention for the first time closes three-dimensional direct writing technology and artificial light zoarium tying, prepares and can be used for three-dimensional direct write skill
The titanate ink of art and the artificial photosystem for successfully realizing printing three-dimensional hierarchical structure；Using three-dimensional direct writing technology, pass through
Structure design can simply prepare the three-dimensional system with different macrostructures and microcosmic hierarchical structure, three-dimensional and classifying porous
Structure is more accurate controllable, and then helps to be promoted the catalytic effect of artificial photosystem；
(2) present invention, which prepares the artificial photosystem of titanate, has the foramen magnum-mesoporous structure of classification, and can be by matching to ink
Regulation and control (the up to 270m of specific surface area is realized in the adjusting of side2g-1) and pore size regulation and control (2-15nm)；
(3) the porous titanate artificial light zoarium architecture of the present invention is adjustable, forms the block structure of different scale, compared to
Powder systems are easy to collect and reuse；
(4) present invention prepares porous titanate artificial light zoarium system CO2Reduction efficiency is significantly improved；
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Description of the drawings
Fig. 1 is that the scanning electron microscope of the 1 three-dimensional porous artificial photosystem of titanium dioxide of gained of the embodiment of the present invention is shone
Piece；
Fig. 2 is the CO of the artificial photosystem of the 1 three-dimensional porous titanium dioxide of gained of present example and its powder2Reduction is surveyed
Examination, CO and CH4Yield block diagram.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit protection scope of the present invention.Those skilled in the art change according to what the present invention made in practical applications
Into and adjustment, still fall within protection scope of the present invention.
In order to better illustrate the present invention, the present invention is described in detail below with attached drawing.
Agents useful for same is all the analytical reagents of sigma-aldrich and Aladdin in following embodiments.
Embodiment 1
2.84g tetraisopropyl titanates and 1g acetylacetone,2,4-pentanediones are added in 10g ethyl alcohol and stir to get mixed solution (this implementation
Example is TiO2System belongs to metatitanic acid salt system special case)；0.5g dodecyl benzene sulfonic acid (DBSA) is added to stir evenly, 0.1g is added
The nanometer silicon dioxide particle ultrasound of a diameter of 15nm is uniformly dispersed for 60 minutes；0.15g polyvinylpyrrolidones and 0.03g is added
Concentrated ammonia liquor simultaneously stirs evenly；Above-mentioned mixed liquor is placed in 80 DEG C of water bath with thermostatic control blenders open heating stirring 8 hours, it is to be mixed
Liquid is concentrated into 10% of stoste or so taking-up and obtains titanium dioxide ink.
Using rotational rheometer (Bohlin Instruments Genmini 200HR), by frequency sweep mode and answer
Power scan pattern measures the viscosity-shear rate curve and modulus-stress curve of the titanium dioxide ink, should known to analysis curve
The storage modulus and loss modulus of ink are 104The Pa orders of magnitude, and storage modulus is more than loss modulus.
The titanium dioxide ink is transferred to 3D printing barrel and installation and 3D printing equipment, the 3D printing equipment are Hangzhoupro
The Einstar-5 type 3D printing systems of three-dimensional Science and Technology Co., Ltd.'s production are first faced in state；3D printing is on albolene matrix
It carries out, vaseline 3D printing substrate need to be made, matrix plays sacrificial layer in roasting process；The albolene matrix by with
It is prepared by lower section method：Albolene is scraped to the quartzy culture dish of a diameter of 200mm；Heating makes albolene melt, and waits for melting completely
Culture dish is moved into 3D printing platform after change；Albolene solidified forming is reduced into plane with temperature；3D printing is 25 in temperature
DEG C, humidity carries out under conditions of being 30%, and the threedimensional model of selection is successively bavin pile model；Printing uses 10 μm of boron glass needles
Head, application pressure are 0.15mPa, print speed 0.8mms-1；2 × 2 × 1mm threedimensional models are completed in printing to be needed 4 hours；It obtains
The threedimensional model obtained has macroscopical macropore (hundreds of microns), and different macrostructures is can behave as by structure design.
Three-dimensional structure is placed in 20 DEG C of air dry ovens after printing and keeps the temperature 24 hours；Then it is roasted at 550 DEG C with Muffle furnace
It burns 4 hours, warming temperature is 5 DEG C/h, forms the mesoporous of diameter about 2nm after roasting in structure；Sample by roasting is immersed
6mol/L potassium hydroxide solutions and 180 DEG C of hydro-thermals 72 hours, form mesoporous (the former SiO of diameter about 12nm after erosion2Nanometer
Grain)；Cleaning 10 times with deionized water after hydro-thermal process makes flushing liquor pH be in neutrality；60 DEG C are dried in vacuo up to three-dimensional porous dioxy
Change the artificial photosystem of titanium, specific surface area 237m2/g。
Fig. 1 is referred to, the electron scanning micrograph of the artificial photosystem of three-dimensional porous titanium dioxide is expressed as, from
It is observed that apparent three-dimensional structure characteristic in figure.From three-dimensional blocky system is macroscopically shown as, hold compared to powder systems
Easily collecting simultaneously reuses.
Comparative example 1
By the artificial photosystem grinding of the three-dimensional porous titanium dioxide of the gained of embodiment 1, obtain powdered three-dimensional porous
The artificial photosystem of titanium dioxide, i.e. abscissa TiO in Fig. 22Powder.
Comparative example 2
Except SiO2Additive amount be 0, other raw material additive amounts and step are same as Example 1, are only added
DBSA is not added with SiO2Titanium dioxide ink printed obtained by the artificial photosystem of three-dimensional porous titanium dioxide, i.e. in Fig. 2
TiO2(DBSA)。
Experiment
The each artificial photosystem CO constructed2Reducing property test carries out in photocatalysis silica ware.Take 50g samples
It is laid in the culture dish of a diameter of 50nm, culture dish is placed in 300mL photocatalysis quartz reactors, photochemical catalyst Au/
RuO2.Entire quartz reaction system is vacuumized, CO is then passed to2Reach atmospheric pressure, be so repeated 3 times, is passed through for the last time
CO2To 0.03mPa, to wait reacting.With aluminium-foil paper encapsulation reaction device, it is protected from light and stands 1h, make sample and CO to be tested2Atmosphere reaches
Adsorption equilibrium.Xe lamps (PerkinElmer, 300W) are opened after 1h, irradiate reactor with ultraviolet-visible.Gas chromatograph simultaneously
(Beijing brilliant science and technology difficult to understand, GC-7920) starts gathered data, acquisition interval 1h.Ultraviolet-visible is obtained after the data processing of acquisition
Light irradiation is lower to restore CO2Generate the yield figure of CO.
Fig. 2 is referred to, the artificial photosystem (TiO of three-dimensional porous titanium dioxide of the printing gained of embodiment 1 is expressed as2
(DBSA/SiO2)), the titania powder (TiO of comparative example 12Powder) and comparative example 2 only addition a DBSA be not added with SiO2's
Artificial photosystem (the TiO of three-dimensional porous titanium dioxide obtained by titanium dioxide ink printed2(DBSA)) in ultraviolet-visible illumination
Penetrate lower reduction CO2The comparison diagram of CO is generated, wherein titania powder contrast sample is the 1 three-dimensional porous titanium dioxide of gained of embodiment
The artificial photosystem grinding of titanium obtains.Compare the two CO yields, it is seen that the three-dimensional porous artificial photosystem CO of titanium dioxide is generated
Speed is faster than titania powder sample, and the three-dimensional porous artificial photosystem CO of titanium dioxide generates the identical specific surface area of speed ratio
Powder Reference's sample it is high by 100% or so, while only addition DBSA be not added with SiO2Titanium dioxide ink printed obtained by three-dimensional
The artificial photosystem specific surface area of poriferous titanium dioxide generates rate comparison titanium dioxide powder with respect to other two kinds of sample smallers, CO
Last sample improves 50%, compared to being added to SiO2The artificial photosystem of three-dimensional porous titanium dioxide then reduce 25%.CO2
Photo-reduction rate improves the promotion for benefiting from printing three-dimensional structure to light capture and gas transport.Thus, it could be seen that the present embodiment is beaten
The three-dimensional porous titanium dioxide artificial light zoarium that print obtains, which ties up to, has good photocatalysis performance in UV-visible range.
Embodiment 2
2.06g strontium acetates are added to 20g ethyl alcohol and stir to get organic solution；2.84g tetraisopropyl titanates and 1g is added
Acetylacetone,2,4-pentanedione stirs to form mixed solution, and the molar ratio of tetraisopropyl titanate and strontium acetate is 1:1；It is total that 0.284g three blocks are added
Polymers-pluronic P123 is stirred evenly, and 120 minutes points of the nanometer silicon dioxide particle ultrasound of a diameter of 50nm of 0.08g is added
It dissipates uniform；0.12g polyvinylpyrrolidones and 0.025g concentrated ammonia liquors is added and stirs evenly；Above-mentioned mixed liquor is placed in 65 DEG C of perseverances
Open heating stirring 12 hours in tepidarium blender, with stirring and solvent volatilization, mixed liquor becomes muddy final from clarifying
Become clarifying again；Obtained concentrate is titanate ink；
It takes out the titanate ink and is transferred to 3D printing barrel with configuration to be printed；3D printing is on albolene matrix
It carries out, print temperature is 25 DEG C, and humidity 40% selects model for successively bavin pile model；Printing uses 30 μm of boron glass syringe needles,
Application pressure is 0.1mPa, print speed 3mms-1；
Three-dimensional structure is placed in 25 DEG C of air dry ovens after printing and keeps the temperature 20 hours；It roasts 6 hours, heats up at 600 DEG C
Temperature is 5 DEG C/h；Sample by roasting is immersed into 6mol/L potassium hydroxide solutions and is placed in 200 DEG C of hydro-thermal axe hydro-thermal 60 hours；
It is cleaned repeatedly and in 60 DEG C of three-dimensional porous artificial photosystems of metatitanic acid strontium of vacuum drying acquisition with deionized water after hydro-thermal process.
Embodiment 3
4.234g strontium nitrates are added to 25g isopropanols stirring long period (about 1 hour) and obtain organic solution；It is added
5.68g tetraisopropyl titanates and 2g acetylacetone,2,4-pentanediones stir to form mixed solution；1.136g triblock copolymers-pluronic is added
F127 is stirred evenly, and F127 dissolves relatively slowly in organic solution, and appropriate heating can be accelerated to dissolve, and is heated to 50 DEG C and is stirred 30 points
Clock；The nanometer silicon dioxide particle ultrasound that a diameter of 30nm of 0.227g are added is uniformly dispersed for 240 minutes；0.227g polyethylene is added
Pyrrolidones and 0.114g concentrated ammonia liquors simultaneously stir evenly；Above-mentioned mixed liquor is placed in 90 DEG C of water bath with thermostatic control blenders open heating
Stirring 12 hours, mixed liquor become muddiness from faint yellow clarification and eventually become buff clarification；Obtained concentrate is titanate
Ink；
The titanate ink is taken out and is transferred to 3D printing barrel with configuration to be printed；3D printing is in albolene matrix
Upper progress, print temperature are 25 DEG C, and humidity 35% selects cellular model；Printing uses 30 μm of boron glass syringe needles, applies pressure
For 0.14mPa, print speed 2.5mms-1；
Three-dimensional structure is placed in 40 DEG C of air dry ovens after printing and keeps the temperature 18 hours；It roasts 6 hours, heats up at 650 DEG C
Temperature is 5 DEG C/h；Sample by roasting is immersed into 6mol/L potassium hydroxide solutions and is placed in 200 DEG C of hydro-thermal axe hydro-thermal 72 hours；
Pure water rinsing repeatedly and in 60 DEG C of vacuum drying obtains the three-dimensional porous artificial photosystem of metatitanic acid strontium after hydro-thermal process.
Embodiment 4
1.58g calcium acetates are added to 15g ethyl alcohol and stir to get organic solution；2.84g tetraisopropyl titanates and 1g is added
Acetylacetone,2,4-pentanedione stirs to form mixed solution, and the molar ratio of tetraisopropyl titanate and calcium acetate is 1:1；0.142g dodecyls are added
Sodium sulphate is simultaneously heated to 60 DEG C and stirs evenly；The nanometer silicon dioxide particle ultrasound of a diameter of 15nm of 0.0284g is added 90 minutes
It is uniformly dispersed；0.17g polyvinylpyrrolidones and 0.057g concentrated ammonia liquors is added and stirs evenly；Above-mentioned mixed liquor is placed in 70 DEG C
Open heating stirring 8 hours in water bath with thermostatic control blender；It is titanate ink to obtain concentration homogenisation liquid；
The obtained titanate ink is taken out and is transferred to 3D printing barrel with configuration to be printed；3D printing is in Bai Fanshi
It is carried out on woods matrix, print temperature is 20 DEG C, and humidity 35% selects model for successively bavin pile model；Printing uses 5 μm of boron glass
Glass syringe needle, application pressure are 0.25mPa, print speed 0.5mms-1；
Three-dimensional structure is placed in 40 DEG C of air dry ovens after printing and keeps the temperature 12 hours；It roasts 6 hours, heats up at 550 DEG C
Temperature is 5 DEG C/h；Sample by roasting is immersed into 6mol/L potassium hydroxide solutions and is placed in 160 DEG C of hydro-thermal axe hydro-thermal 72 hours；
Pure water rinsing repeatedly and in 60 DEG C of vacuum drying obtains the three-dimensional porous artificial photosystem of metatitanic acid calcium after hydro-thermal process.
Embodiment 5
3.79g lead acetates are added to 10g n-butanols and stir to get organic solution；Be added 2.84g tetraisopropyl titanates and
1g acetylacetone,2,4-pentanediones stir to form mixed solution；0.71g cetyl trimethylammonium bromides are added to stir evenly, it is straight that 0.284g is added
The nanometer silicon dioxide particle ultrasound that diameter is 30nm is uniformly dispersed for 180 minutes；0.15g polyvinylpyrrolidones and 0.02g is added
Concentrated ammonia liquor simultaneously stirs evenly；Above-mentioned mixed liquor is placed in 90 DEG C of water bath with thermostatic control blenders open heating stirring 6 hours；It obtains
Even concentrate is titanate ink；
The obtained titanate ink is taken out and is transferred to 3D printing barrel with configuration to be printed；3D printing is in Bai Fanshi
It is carried out on woods matrix, print temperature is 30 DEG C, and humidity 50% selects model for successively bavin pile model；Printing uses 30 μm of boron
Glass syringe needle, application pressure are 0.12mPa, print speed 2.5mms-1；
Three-dimensional structure is placed in 30 DEG C of air dry ovens after printing and keeps the temperature 15 hours；It roasts 4 hours, heats up at 650 DEG C
Temperature is 5 DEG C/h；Sample by roasting is immersed into 6mol/L potassium hydroxide solutions and is placed in 200 DEG C of hydro-thermal axe hydro-thermal 60 hours；
Pure water rinsing is repeatedly after hydro-thermal process and 80 DEG C of vacuum drying obtain three-dimensional porous lead titanates artificial light zoarium system.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to preferably explain the present invention
Principle and practical application, to enable skilled artisan to be best understood by and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (10)
1. a kind of preparation method of titanate ink, which is characterized in that include the following steps：
S1：The salt compounds of metal A are dissolved in organic solvent B, organic solution is obtained；The metal A is selected from metal Sr,
One kind in Ca, Pb, the one kind of organic solvent in ethyl alcohol, isopropanol, n-butanol；
S2：Tetraisopropyl titanate and acetylacetone,2,4-pentanedione are added into the organic solvent that step S1 is obtained, is mixed after stirring
Solution I；
S3：The surfactant C into the mixed solution I that step S2 is obtained is uniformly mixed, obtains mixed solution II；
S4：Nanometer silicon dioxide particle is added into the mixed solution II, is cleaned by ultrasonic, obtains mixed solution III；
S5：Polyvinylpyrrolidone (PVP) and concentrated ammonia liquor are added into the mixed solution III, obtains mixed solution IV；
S6：The concentration of IV solvent flashing of the mixed solution is obtained into the titanate ink.
2. the preparation method of titanate ink as described in claim 1, which is characterized in that live on surface described in the step S3
Property agent C be selected from triblock copolymer-pluronic F127 (F127), triblock copolymer-pluronic P123 (P123), 12
Sodium alkyl sulfate (SDS), cetyl trimethylammonium bromide (CTAB), one kind in dodecyl benzene sulfonic acid (DBSA).
3. the preparation method of titanate ink as described in claim 1, which is characterized in that the tetraisopropyl titanate and described
The molar ratio of metal A is consistent with gained titanate corresponding element atomic ratio, the salt compounds of the metal A and organic solvent
The molar ratio of the preferred 10-80% of mass ratio, tetraisopropyl titanate and acetylacetone,2,4-pentanedione is 50%；The surfactant C and metatitanic acid
The mass ratio of tetra-isopropyl is 5-25%, and the mass ratio of nanometer silicon dioxide particle and tetraisopropyl titanate is 1-10%；It is described
The preferred 4-6% of the mass ratio of polyvinylpyrrolidone and tetraisopropyl titanate；The quality of the concentrated ammonia liquor and tetraisopropyl titanate
Than preferred 1-2%.
4. the preparation method of titanate ink as claimed in claim 3, which is characterized in that nanometer two described in the step S4
Silicon oxide particle size is 15nm, 30nm or 50nm.
5. the preparation method of titanate ink as described in claim 1, which is characterized in that metal A described in the step S1
Addition be 0, the titanate ink that step S6 is obtained is titanium dioxide ink.
6. the preparation method of titanate ink as described in claim 1, which is characterized in that the volume of the concentrated liquid in the step S6
When reaching the 10-20% of former mixed liquor volume, the use of titanate ink can be used as.
7. the preparation method of titanate ink as described in claim 1, which is characterized in that the titanate ink is solid in half
State, storage modulu and loss modulus are 104The Pa orders of magnitude, and storage modulu is more than loss modulus.
8. a kind of method of the porous titanate artificial light zoarium system of printing, which is characterized in that include the following steps：
T1：Titanate ink is transferred to 30mL polypropylene 3D printing barrels；It is installed in 3D printing equipment and is transmitted with air pressure
Device connects；Boron glass syringe needle is connected on 3D printing barrel；
T2：Printing path is set by the titanate ink printed into three-dimensional knot by writing G-code code drawing three-dimensional models
Structure, print procedure carry out on plane vaseline matrix, and temperature is 20-30 DEG C, humidity 30-50%, pressure 0.1-
0.3mPa, syringe needle movement speed are 0.5-3mms-1；
T3：The three-dimensional structure that printing is constructed is transferred to air dry oven, 20-40 DEG C keeps the temperature 12-24 hours；
T4：Titanate three-dimensional structure is roasted 4-6 hours in 500-650 DEG C；
T5：Three-dimensional structure after roasting is immersed into 6mol/L potassium hydroxide solutions and is placed in water heating kettle, 160-200 DEG C of heat preservation 48-
72 hours, washing and drying was up to the artificial photosystem of titanate with three-dimensional structure.
9. the method for printing porous titanate artificial light zoarium system as claimed in claim 8, which is characterized in that the step T1
In the titanate ink be selected from claim 1-7 any claims obtained by titanate ink.
10. the method for printing porous titanate artificial light zoarium system as claimed in claim 8, which is characterized in that the metatitanic acid
The artificial photosystem specific surface area of salt is 150-270m2/ g is classified mesoporous containing 2-25nm.
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Application publication date: 20181102 |