CN108543529A - A kind of preparation method for helping oxidative degradation additive with special appearance - Google Patents
A kind of preparation method for helping oxidative degradation additive with special appearance Download PDFInfo
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- CN108543529A CN108543529A CN201810355535.9A CN201810355535A CN108543529A CN 108543529 A CN108543529 A CN 108543529A CN 201810355535 A CN201810355535 A CN 201810355535A CN 108543529 A CN108543529 A CN 108543529A
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- titanium dioxide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000654 additive Substances 0.000 title claims abstract description 21
- 230000000996 additive effect Effects 0.000 title claims abstract description 21
- 238000010525 oxidative degradation reaction Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 210000003462 vein Anatomy 0.000 claims abstract description 48
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 36
- 238000001354 calcination Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- -1 Titanium alkoxides Chemical class 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 229920000704 biodegradable plastic Polymers 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 235000019083 Osmanthus fragrans Nutrition 0.000 description 6
- 244000242564 Osmanthus fragrans Species 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000006065 biodegradation reaction Methods 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003244 pro-oxidative effect Effects 0.000 description 2
- 230000001932 seasonal effect Effects 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 239000008380 degradant Substances 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of preparation methods for helping oxidative degradation additive titanium dioxide with special appearance, and this method comprises the following steps：S1. leaf is cleaned up, removes mesophyll and obtains vein template；S2. rudimentary Titanium alkoxides are added in alcoholic solution, stir to get clear solution；S3. the clear solution in S2 is slowly dropped in the mixed solution of alcohol and acid, stirs to get precursor solution；S4. the vein template in S1 is impregnated in the precursor solution in S3, the vein template after cleaning dipping obtains the titanium dioxide of special appearance after drying calcination.The preparation method obtains the vein biological template with abundant hollow structure and great porosity by removing mesophyll, and rudimentary Titanium alkoxides are fully hydrolyzed in the internal structure of vein under acid condition, significantly improve the appearance structure of titanium dioxide.Titanium dioxide optical catalyst prepared by the preparation method of the present invention has special pattern and catalytic performance excellent, is expected to use as efficient degradation additive in oxidized-biodegradable plastic.
Description
Technical field
The present invention relates to photocatalysis to help the preparation method of oxidative degradation additive more particularly to a kind of with special appearance
Help the preparation method of oxidative degradation additive titanium dioxide.
Background technology
" white pollution " caused by waste plastic has become global environment difficulties, and degradative plastics faces new opportunity.Oxygen
Change-biodegradation (oxo-biodegradation) technology is since it is strong with normal temperature oxidation degradation capability, thorough mineralising, low energy
Consumption, environmentally friendly feature and widely paid attention to.In recent years, oxidation-biodegradation is considered as maximally efficient, economic degradation
One of technology.Oxidation-biodegradation process includes two stages：The oxidation fragmentation of first stage and the biology drop of second stage
Solution.Moreover, research shows that the speed of degradation process depends on the oxidation by helping oxidation additive (Pro-oxidants) to be induced
Stage of fragmentation.As it can be seen that the exploitation and development of efficient degradation pro-oxidant, are the key that obtain such oxidation-biodegradable plastic.
Currently, biological template method because its mould material is abundant, economic and environment-friendly, preparation method simply become prepare it is porous, high
One of key technologies of materials such as surface area, pattern be special, have caused the highest attention of researcher.It is cereal pollen, all kinds of
Timber, rattan trunk and straw etc. were all once used as the porous material that hard template prepares various structures.But cereal pollen, straw have
Body is seasonal, and wood type generally requires crushing and screening, and vein has master pulse, lateral vein and thready pulse, is separated on master pulse many smaller
Lateral vein is divided into out more tiny thready pulse on lateral vein, and last vein system is unified into reticular structure, is that leaf median nexus is at most and rich
Richness is easy to get, it is only necessary to do simple process can be used as template, and leaf take naturally, measuring big asepsis environment-protecting.Therefore it provides one
Kind prepares the titanium dioxide with special appearance and with high efficiency photocatalysis activity with extremely important using vein as biological template
Meaning.
Invention content
The present invention is directed to overcome in biological template in the prior art seasonal limitation and complex pretreatment, one is provided
The preparation method that helps oxidative degradation additive titanium dioxide of the kind with special appearance.
The purpose of the present invention is to provide a kind of titanium dioxide with special appearance prepared according to this method.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
S1. leaf is cleaned up, removal mesophyll obtains vein template；
S2. rudimentary Titanium alkoxides are added in alcoholic solution, stir to get clear solution；
S3. the clear solution in S2 is slowly dropped in the mixed solution of alcohol and acid, before being obtained after 30~70min of stirring
Liquid solution is driven, sour and alcohol volume ratio is 2:4~2:6, sour a concentration of 4~10mol/L；
S4. the vein template in S1 is impregnated in the precursor solution in S3,10~80h of dip time, cleaning dipping
Vein template afterwards obtains the titanium dioxide of special appearance after drying calcination.
The vein of leaf has master pulse, lateral vein and thready pulse, and many smaller lateral veins are separated on master pulse, is divided into out on lateral vein thinner
Small thready pulse, last vein system are unified into reticular structure, have abundant hollow structure and great porosity.Using leaf as
Biological template prepares titanium dioxide, and in acid condition, rudimentary Titanium alkoxides are fully hydrolyzed in the internal structure of vein, are obtained
Titanium dioxide with vein special appearance and high efficiency photocatalysis activity.
The presence of mesophyll can influence the formation of titanium dioxide special appearance, and mesophyll removal processing must be carried out before dipping.Leaf
The content of meat is fewer, is more conducive to solution and enters in the internal structure of vein, more advantageously forms the TiO with vein pattern2
Powder.
Preferably, in the S1 vein template be without any mesophyll pure vein template.
Preferably, the calcination time is in the S4：45~200min；Calcination temperature is：500~900 DEG C.Suitable dipping
Time, calcination time and calcination temperature can just prepare the good titanium dioxide of pattern.
It is highly preferred that it is 60~120min to be calcined the time in the S4；Calcination temperature is 500~700 DEG C.
Preferably, rudimentary Titanium alkoxides are butyl titanate in the S2.
Preferably, alcohol is absolute ethyl alcohol in the S2.
Preferably, the volume ratio of rudimentary Titanium alkoxides and alcohol is in the S2：1~4:6~12.
Preferably, mixing time is 20~80min in the S2.
Preferably, the acid in the S3 is nitric acid.Due to the presence of nitric acid, hydrogen ion can inhibit its speed hydrolyzed,
Butyl titanate will not decompose immediately with the contact with moisture in leaf, while ligand of the nitrate anion as butyl titanate, also may be used
To play stabilization.Relative to weak acid, the nitric acid of the amount concentration of same substance can dissociate more hydrogen ions, relative to it
For his strong acid, there is nitrate anion can be as the ligand of butyl titanate.
Preferably, dip time is 60h in the S4.
Mesophyll minimizing technology is that aqueous slkali boils processing in the S1, and lye mass fraction is 5%~20%, boiling time
0.5~5h.The lye can be sodium hydroxide solution, using lye boil can be simple and convenient removal vein mesophyll, fill
Divide the vein network for showing leaf template, provides better template for the preparation of specially-shaped titanium dioxide, obtain special form
The titanium dioxide of looks provides more possibility to obtain the degradant additive with high efficiency photocatalysis activity.
It is a kind of to help oxidative degradation additive titanium dioxide with special appearance by prepared by above-mentioned preparation method.
The present invention has the advantages that compared with the existing technology：
The present invention provides a kind of preparation methods for helping oxidative degradation additive titanium dioxide with special appearance, pass through
Removal mesophyll obtains having the vein biological template for enriching hollow structure and great porosity, rudimentary Titanium alkoxides under acid condition
It is fully hydrolyzed in the internal structure of vein, significantly improves the appearance structure of titanium dioxide.The preparation method system of the present invention
Standby titanium dioxide optical catalyst has special pattern and efficient photocatalytic activity, can be in oxidation-biodegradable plastic
It is used as efficient degradation additive.
Description of the drawings
Fig. 1 is that ((a) is the sample real scene shooting figure after the calcination of comparative example 1 for the sample drawing of real scene shooting after calcination；(b) it is comparative example 2
Biological template；(c) it is the biological template of comparative example 3；(d) it is the biological template of embodiment 1).
Fig. 2 is that the SEM of the pure vein biological template of embodiment 1 schemes
Fig. 3 is the SEM figures for the titanium dioxide that embodiment 1 is prepared.
Fig. 4 is the SEM figures for the titanium dioxide that comparative example 1 is prepared.
Fig. 5 is the SEM figures for the titanium dioxide that comparative example 3 is prepared.
Fig. 6 is the EDS figures for the titanium dioxide that embodiment 1 is prepared.
Fig. 7 is the XRD diagram of sample in P25 and embodiment 1.
Specific implementation mode
Further illustrated the present invention below in conjunction with specific embodiment, but embodiment the present invention is not done it is any type of
It limits.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagent, methods and apparatus.
Unless stated otherwise, agents useful for same and material of the present invention are purchased in market.
Examples 1 to 8
A kind of preparation method for helping oxidative degradation additive titanium dioxide with special appearance, includes the following steps：
S1. leaf is cleaned up, removes mesophyll and obtains vein template：A certain amount of sweet osmanthus leaf is picked, is cleaned with clear water
Afterwards with deionized water clean 3 times it is spare, prepare mass fraction be 10% sodium hydroxide solution, sodium hydroxide solution is placed in pad
Have on the electric furnace of asbestos gauge, is heated to boiling.Solution boiling after suitable sweet osmanthus leaf is added, boil it is soft rotten to mesophyll, with clean hair
Brush handle mesophyll brushes, and deionized water is cleaned to solution and clarified, and pure vein is obtained, spare；
S2. 10mL butyl titanates are added in 60mL absolute ethyl alcohols, stir 30min, obtains light yellow transparent solution；
S3. the clear solution in S2 is slowly dropped in the mixed solution of alcohol and acid, presoma is obtained after stirring 30min
Solution；
S4. the vein template in S1 is impregnated in the precursor solution in S3, is impregnated at normal temperatures and pressures, take out leaf
Arteries and veins, deionization are washed till solution clarification, and the vein after 60 DEG C of dryings is placed in Muffle furnace, and calcination obtains vein special appearance titanium dioxide
Titanium.
Specific experiment parameter setting see the table below 1：Wherein A is the volume ratio of acid and alcohol in mixed solution sour in S3；B is
Sour concentration in S3；C is dip time in S4, h；D is calcination temperature in S4, DEG C；E is calcination time in S4, and h, F are hydrogen in S1
Sodium oxide molybdena processing time.
Wherein Examples 1 to 7 is sweet osmanthus leaf, and embodiment 9 is Flos micheliae Albae leaf.
| Serial number | A | B | C | D | E | F |
| Embodiment 1 | 2:5 | 6 | 60 | 600 | 2 | 3 |
| Embodiment 2 | 2:5 | 6 | 10 | 600 | 2 | 3 |
| Embodiment 3 | 2:5 | 6 | 72 | 600 | 2 | 3 |
| Embodiment 4 | 2:5 | 6 | 60 | 700 | 2 | 3 |
| Embodiment 5 | 2:5 | 6 | 60 | 500 | 2 | 3 |
| Embodiment 6 | 2:5 | 6 | 60 | 600 | 0.75 | 3 |
| Embodiment 7 | 2:5 | 6 | 60 | 600 | 2 | 1 |
| Embodiment 8 | 2:5 | 6 | 60 | 600 | 1 | 3 |
| Embodiment 9 | 2:5 | 6 | 60 | 600 | 2 | 3 |
| Embodiment 10 | 2:5 | 6 | 60 | 900 | 2 | 3 |
Comparative example 1
10mL butyl titanates are added in 60mL absolute ethyl alcohols, 30min is stirred, obtains light yellow transparent solution；It will
Light yellow transparent solution is slowly dropped into the mixed solution of absolute ethyl alcohol containing 40mL and 40mL nitric acid (6mol/L), is quickly stirred
30min obtains precursor solution, and the sweet osmanthus leaf that processing is not boiled by NaOH solution is placed in precursor solution,
72h is impregnated under normal temperature and pressure, takes out vein, and deionization is washed till solution clarification.Vein after 60 DEG C of dryings is placed in Muffle furnace,
It is calcined 2h at 600 DEG C, obtains titanium dioxide.
Comparative example 2~6
Essentially identical with the operating procedure of embodiment 1, design parameter is shown in Table 2.
| Serial number | A | B | C | D | E | F |
| Comparative example 2 | 2:3 | 6 | 60 | 600 | 2 | 3 |
| Comparative example 3 | 2:5 | 6 | 8 | 600 | 2 | 3 |
| Comparative example 4 | 2:5 | 6 | 60 | 600 | 0.5 | 3 |
| Comparative example 5 | 2:5 | 6 | 60 | 200 | 2 | 3 |
| Comparative example 6 | 2:5 | 6 | 60 | 1000 | 2 | 3 |
Experimental result
In terms of comparative example 1~the 3 as different from Example 1 pretreatment of biological template, biological template is adopted in comparative example 1
It is the biological template removed without mesophyll, comparative example 2 is boiled 1h deionizations using sodium hydroxide and cleaned to solution
Clear sweet osmanthus leaf (mesophyll not boiling), comparative example 3 using sodium hydroxide boil deionization after 2.5h clean it is clear to solution
Clear sweet osmanthus leaf (containing mesophyll and vein simultaneously), while dip time is slightly long (72h), synthesis phase is shown, in comparative example 1,2
With vein specially-shaped titanium dioxide cannot be obtained under 3 preparation condition.
Fig. 1 (a) is the biological template of comparative example 1；(b) it is the biological template of comparative example 2；(c) it is the biological mould of comparative example 3
Plate；(d) it is the biological template of embodiment 1.Using comparative example 1, without the leaf by 10%NaOH solution, (i.e. mesophyll is all deposited
) be the sample that is prepared of template it is the canescence block with black splotch, with the leaf of comparative example 2 and comparative example 3
It is greyish white color substance for the sample that template is prepared, is prepared into for template with 1 pure vein of embodiment (i.e. mesophyll all removes)
The sample arrived is pure white filiform.
Fig. 2~6 are the SEM figures to leaf progress different pretreatments and the EDS figures that pure vein is biological template.Wherein Fig. 2
For the SEM figures of the pure vein biological template of embodiment 1, Fig. 3 is the SEM figures for the titanium dioxide that embodiment 1 is prepared, and Fig. 4 is
The SEM for the titanium dioxide that comparative example 1 is prepared schemes, and Fig. 5 is the SEM figures for the titanium dioxide that comparative example 3 is prepared, and Fig. 6 is
The EDS for the titanium dioxide that embodiment 1 is prepared schemes.It can be seen from the figure that the titanium dioxide of comparative example 1 being prepared is
Block, size differ, and little particle is carried on the surface of bulk, and shape is irregular；The titanium dioxide that comparative example 3 is prepared is
The irregular block of shape；Titanium dioxide prepared by embodiment 1 is the shape for having nervate special appearance structure and pure vein
Looks are extremely similar.SEM figures illustrate that the pattern handling result of biological template determines the TiO being prepared2Pattern, EDS figure say
The bright substance being prepared is strictly TiO2Rather than biological template itself.
Fig. 7 is XRD diffraction patterns, wherein (a) is the XRD diffraction patterns for being commercialized P25, (b) two be prepared for embodiment 1
The XRD diffraction patterns of titanium oxide.By compareing X-ray diffraction standard card JCPDS No.21-1272, JPCDS NO.21-1276
With JCPDS No.47-1743 it is found that 2 θ values are 25.3 (101), 37.9 (103), 48.0 (200), 54.6 (105) and 62.8
(204) corresponding TiO2The diffraction maximum of anatase；2 θ values are 27.44 (110), 6.08 (101), 41.22 (111), 56.64 (220)
TiO2Corresponding Rutile Type diffraction maximum；The sample that embodiment 1 is prepared is anatase and rutile mixing crystal form TiO2(AR) powder
End.Rutile and anatase crystal can play synergistic effect, and catalytic effect is better than single crystal form titanium dioxide.
To the degradation rate of methyl orange under titanium dioxide the same terms that Examples 1 to 10 and comparative example 1~6 are prepared
| Serial number | 10min (%) | 20min (%) | 30min (%) | 40min (%) | 50min (%) |
| Embodiment 1 | 17.46 | 36.26 | 54.74 | 71.96 | 87.49 |
| Embodiment 2 | 23.56 | 47.116 | 67.52 | 84.55 | 97.15 |
| Embodiment 3 | 17.82 | 36.542 | 52.932 | 68.35 | 84.44 |
| Embodiment 4 | 20.37 | 41.71 | 64.01 | 81.19 | 95.25 |
| Embodiment 5 | 22.89 | 44.14 | 63.58 | 82.96 | 94.89 |
| Embodiment 6 | 27.09 | 53.16 | 75.72 | 96.10 | 99.45 |
| Embodiment 7 | 37.24 | 72.69 | 92.56 | 99.92 | 99.61 |
| Embodiment 8 | 18.66 | 37.69 | 54.98 | 72.28 | 84.37 |
| Embodiment 9 | 34.34 | 63.21 | 83.53 | 96.49 | 97.76 |
| Embodiment 10 | 20.47 | 39.16 | 54.14 | 68.33 | 81.81 |
| Comparative example 1 | 7.82 | 8.72 | 12.48 | 16.62 | 20.92 |
| Comparative example 2 | 11.76 | 24.69 | 35.59 | 46.57 | 58.18 |
| Comparative example 3 | 12.25 | 25.28 | 37.96 | 52.89 | 66.34 |
| Comparative example 4 | 15.93 | 33.66 | 49.81 | 64.69 | 78.14 |
| Comparative example 5 | 4.67 | 9.49 | 15.17 | 19.70 | 25.38 |
| Comparative example 6 | 2.73 | 5.60 | 8.33 | 11.20 | 13.85 |
As seen from the above table, the sample in embodiment reaches 84% in ultraviolet lighting 50min to the degradation rate of methyl orange
More than, efficiency is highest up to 99.61%, close to 100%, can theoretically accelerate the degradation of organic matter.Therefore, control can be passed through
Implementation condition adjusts degradation rate to regulate and control the be degraded service life of object, such as agricultural film, plastic products etc. in a certain range.
Embodiment of the present invention are not limited by the above embodiments, and other any spirit without departing from the present invention are real
Changes, modifications, substitutions, combinations, simplifications made by under matter and principle, should be equivalent substitute mode, are included in the present invention
Protection domain within.
Claims (9)
1. a kind of preparation method for helping oxidative degradation additive titanium dioxide with special appearance, which is characterized in that including such as
Lower step：
S1. leaf is cleaned up, removes mesophyll and obtains vein template；
S2. rudimentary Titanium alkoxides are added in alcoholic solution, stir to get clear solution；
S3. the clear solution in S2 is slowly dropped in the mixed solution of alcohol and acid, presoma is obtained after stirring 30 ~ 70min
The volume ratio of solution, acid and alcohol is 1:2~1:3, sour a concentration of 4 ~ 10mol/L；
S4. the vein template in S1 is impregnated in the precursor solution in S3,10 ~ 80h of dip time, after cleaning dipping
Vein template, drying calcination obtain the titanium dioxide of special appearance after removing vein.
2. the preparation method for helping oxidative degradation additive titanium dioxide with special appearance as described in claim 1, feature
It is, it is 45 ~ 200min that the time is calcined in the S4；Calcination temperature is 500 ~ 900 DEG C.
3. the preparation method for helping oxidative degradation additive titanium dioxide with special appearance as described in claim 1, feature
It is, it is 60 ~ 120min that the time is calcined in the S4；Calcination temperature is 500 ~ 700 DEG C.
4. the preparation method for helping oxidative degradation additive titanium dioxide with special appearance as described in claim 1, feature
It is, rudimentary Titanium alkoxides are butyl titanate in the S2.
5. the preparation method for helping oxidative degradation additive titanium dioxide with special appearance as described in claim 1, feature
It is, alcohol is absolute ethyl alcohol in the S2.
6. the preparation method for helping oxidative degradation additive titanium dioxide with special appearance as described in claim 1, feature
It is, the volume ratio of rudimentary Titanium alkoxides and alcohol is 1 ~ 4 in the S2:6~12.
7. the preparation method for helping oxidative degradation additive titanium dioxide with special appearance as described in claim 1, feature
It is, the acid in the S3 is nitric acid.
8. the preparation method for helping oxidative degradation additive titanium dioxide with special appearance as described in claim 1, feature
It is, mesophyll minimizing technology is that aqueous slkali boils processing in the S1, and lye mass fraction is 5% ~ 20%, boiling time 0.5 ~
5h。
9. a kind of help oxidative degradation to add by prepared by any one of the claims 1 ~ 8 preparation method with special appearance
Add agent titanium dioxide.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101491756A (en) * | 2009-03-05 | 2009-07-29 | 上海交通大学 | Preparation method of titanium dioxide photocatalyst of plant graded structure |
| CN103073055A (en) * | 2011-10-25 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Process for preparing titanium dioxide with network structure by using biological template method |
| WO2014006409A1 (en) * | 2012-07-03 | 2014-01-09 | Brunel University | Method of making metal oxide catalysts using templates |
-
2018
- 2018-04-19 CN CN201810355535.9A patent/CN108543529B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101491756A (en) * | 2009-03-05 | 2009-07-29 | 上海交通大学 | Preparation method of titanium dioxide photocatalyst of plant graded structure |
| CN103073055A (en) * | 2011-10-25 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Process for preparing titanium dioxide with network structure by using biological template method |
| WO2014006409A1 (en) * | 2012-07-03 | 2014-01-09 | Brunel University | Method of making metal oxide catalysts using templates |
Non-Patent Citations (2)
| Title |
|---|
| 李建强等: "树叶为模板网状TiO2的制备及其光催化性能", 《化学学报》 * |
| 黄晶晶: "植物仿生碳/氧化物复合材料制备与光还原性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809480A (en) * | 2019-02-28 | 2019-05-28 | 华南农业大学 | A kind of preparation method of anatase crystal titanium dioxide and its titanium dioxide of preparation |
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