CN109878069A - A kind of dendritic phthalocyanine@SiO2The preparation method of photocatalytic device - Google Patents
A kind of dendritic phthalocyanine@SiO2The preparation method of photocatalytic device Download PDFInfo
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- CN109878069A CN109878069A CN201910110285.7A CN201910110285A CN109878069A CN 109878069 A CN109878069 A CN 109878069A CN 201910110285 A CN201910110285 A CN 201910110285A CN 109878069 A CN109878069 A CN 109878069A
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Abstract
The present invention discloses a kind of dendritic phthalocyanine@SiO2The preparation method of photocatalytic device, be made by following methods: preparation can pore-creating wire rod and high light transmission wire rod, can pore-creating wire rod be printed as device frame, high light transmission wire rod prints upper and lower panel, photochemical catalyst post package is loaded in device inside again, obtains 3D printing photocatalytic device.The present invention frees in and out contaminant molecule using frame porosity, and powder photocatalysis is prevented to spread, and solves the problems, such as difficult withdrawal, preparation method is simple, and low in cost, device is reusable, and photocatalysis effect is preferable.
Description
Technical field
The invention belongs to environmental treatment technical fields, and in particular to a kind of dendritic phthalocyanine@SiO2The system of photocatalytic device
Preparation Method.
Background technique
As process of industrialization accelerates, energy shortage and problem of environmental pollution become increasingly conspicuous.Water pollution is always one
Serious environmental problem, even micro heavy, dyestuff, drug are all great to human body damage in water body.At water pollution
There are many reason method, and wherein photocatalysis technology is a kind of effective ways that problem of environmental pollution is solved using new energy, it is utilized
Photocatalytic degradation poisonous and harmful substance provides a kind of very environment protection treating pollution method.But current most of photochemical catalyst
For powder, hardly possible recycling becomes a great problem for limiting its application, and device is then the feasible method for solving this problem.
Chinese patent ZL2014108005249 discloses a kind of 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2It can
The preparation method and applications of light-exposed photochemical catalyst, dendritic phthalocyanine described in patent load SiO2Active oxygen yield
The advantages that height, good hydrophilic property, high not easy to reunite and electronics transfer rate, it can be applied to Industrial Waste Water Treatments, degradation of dye waste water etc.
Field.But the dendritic phthalocyanine of solid-state powdery loads SiO2There are problems that device and recycling in practical applications
At present realize device method it is very much, such as by catalyst be coated in a variety of materials surface, CN201510118618.2 with
CN201510118543.8 discloses the preparation method and coating method of two kinds of coating agent of photocatalysis, this method load factor compared with
Height, but complex and immobilized catalyst is easy to fall off.Also have and various photocatalysis are made with the direct melt blending of high molecular material
Material, this method is relatively simple, but catalyst is largely coated on inside macromolecule, causes to waste.
3D printing is a kind of novel intelligent increases material manufacturing technology, is compared compared to traditional molding mode, have quickly preparation,
The advantages that fining manufacture, stock utilization height, product structure can design.Wherein fused glass pellet (FDM) is popularized the most
3D printing technique, high molecular material can be printed as the device of labyrinth by it, to meet the different demands of different application.
The container of " button cell " formula of design, the top and bottom of button are formed by high light transmission resin material through 3D printing, and knob
The frame of button by can pore forming material print, formed into the water porous, realize the free entry and exit of dye molecule, prevent powder
Photocatalysis diffusion solves the problems, such as difficult withdrawal.Preparation method is simple, low in cost, and device is reusable, photocatalysis effect
It is good.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of dendritic phthalocyanine@SiO2Photocatalytic device
Preparation method.In order to achieve the object of the present invention, specific technical solution is as follows:
A kind of dendritic phthalocyanine@SiO2The preparation method of photocatalytic device, comprising the following steps:
(1) it is granulated after according to the ratio mixing plastic basis material, water-soluble pore creating material by screw rod melting extrusion, gained pellet is passed through
For wire rod machine travel at 3D printing wire rod, obtaining can pore-creating wire rod；
(2) high light transmission resin is granulated by screw rod melting extrusion, by gained pellet by wire rod machine travel at 3D printing wire rod,
Obtain high light transmission wire rod；
(3) by more material 3D printer integrations print, by obtained in step (1) can pore-creating wire rod be printed as device side
Frame, high light transmission wire rod obtained in step (2) print upper and lower panel, then internal sky is formed by between the upper and lower panel of device
1-3 is loaded in chamber loads SiO for aryl oxide dendritic phthalocyanine complex2Post package obtains 3D printing photocatalytic device, can pore-creating wire rod
The device frame being printed as can form porous into the water, realize the free entry and exit of dye molecule, and powder light can be prevented to urge
Change diffusion, solves the problems, such as difficult withdrawal.
The water-soluble pore creating material is one or more of in PVP, PVA, sucrose, NaCl, sodium carbonate.
The proportion of plastic basis material and water-soluble pore creating material in the step (1) are as follows: 60 ~ 95 parts of plastic basis material, water-soluble
20 ~ 40 parts of pore creating material.
The plastic basis material is selected from polylactic acid (PLA), polycaprolactone (PCL), two rouge of poly-succinic fourth (PBS), gathers oneself
Diacid/butylene terephthalate (PBAT), acrylonitrile-butadiene-styrene (ABS) plastics (ABS), polypropylene (PP), polyethylene
One of (PE) or it is a variety of.
The high light transmission resin is selected from polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PETG), heat
Plastic polyurethane elastomer rubber (TPU), polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PCTG), poly- first
One of base methyl acrylate (PMMA) is a variety of.
The dendritic phthalocyanine@SiO2 photocatalytic device is applied to catalytic degradation phenol.
After adopting the above technical scheme, the present invention have the advantages that following features and: 1, preparation method is simple and efficient, and device can
Recycling；2, the recycling of powder photocatalyst difficulty is solved the problems, such as；3, it can apply to catalytic degradation phenol.
Detailed description of the invention
Fig. 1 is using dendritic phthalocyanine@SiO prepared by the embodiment of the present invention 12Two of photocatalytic device can cover one
Rise and the different shell comparison diagram of size.
Fig. 2 is using dendritic phthalocyanine@SiO prepared by the embodiment of the present invention 12Photocatalytic device catalytic degradation benzene twice
Phenol active control figure.
Fig. 3 is using dendritic phthalocyanine@SiO prepared by the embodiment of the present invention 12Photocatalytic device is catalyzed the 3rd degradation
Phenol activity figure.
Specific embodiment
Embodiment 1
(1) it is granulated after mixing 6kg PLA, 4kg PVA by screw rod melting extrusion, double screw extruder parameter an are as follows: area 100
DEG C, two 110 DEG C of areas, three 130 DEG C of areas, four 140 DEG C of areas, five 150 DEG C of areas, six 160 DEG C of areas, seven 170 DEG C of areas, eight 170 DEG C of areas, 9th area
160 DEG C, 150 DEG C of die head, revolving speed is 200 rpm, and extruding pelletization obtains wire rod master batch, and gained pellet is passed through wire rod machine travel
At 3D printing wire rod, wire rod machine parameter are as follows: 160 DEG C of an area, two 170 DEG C of areas, three 170 DEG C of areas, four 160 DEG C of areas, revolving speed 50
Rpm, the silk cooling by water of extrusion by traction machine travel and control wire vent line footpath 1.75mm, and obtaining can pore-creating wire rod；
(2) 10kg PETG is passed through into wire rod machine travel into 3D printing wire rod, wire rod machine parameter are as follows: 200 DEG C of an area, two areas 210
DEG C, three 200 DEG C of areas, four 200 DEG C of areas, revolving speed is 50 rpm, and the silk cooling by water of extrusion by traction machine travel and controls wire vent
Line footpath 1.75mm obtains high light transmission wire rod；
(3) by more material 3D printer integrations print, by obtained in step (1) can pore-creating wire rod be printed as device side
Frame, 180 DEG C of print temperature, high light transmission wire rod obtained in step (2) prints upper and lower panel, and 230 DEG C of print temperature, then in device
Inside loads 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2Post package obtains dendritic phthalocyanine@SiO2Photocatalytic device.
It (is placed in double glazing collet (logical condensed water), optical filter guarantees incident light wave using 500 w tungsten halogen lamps as light source
Long λ is between 420-800 nm), it is 1.35 × 10 in 250mL concentration-4Dendroid phthalein is added in the phenol solution of mol/L
Cyanines@SiO2Photocatalytic device (2.0g) carries out photocatalytic degradation experiment, and phenol solution is taken to carry out ultraviolet-visible light per hour
Spectrum analysis (determines that phenol solution concentration changes in degradation process according to light absorption value at 233 nm of sample), amounts to 5 hours；It returns
It receives product to be repeated twice according to the above method, obtains dendritic phthalocyanine@SiO2Photocatalytic device is catalyzed twice under visible light conditions
Degradation of phenol activity figure, specific 3rd catalytic degradation phenol activity figure as shown in Figure 2 and as shown in Figure 3.
Embodiment 2
(1) it is granulated after mixing 7kg PLA, 3kg NaCl by screw rod melting extrusion, double screw extruder parameter an are as follows: area
100 DEG C, two 110 DEG C of areas, three 130 DEG C of areas, four 140 DEG C of areas, five 150 DEG C of areas, six 160 DEG C of areas, seven 170 DEG C of areas, eight 170 DEG C of areas,
Nine 160 DEG C of areas, 150 DEG C of die head, revolving speed is 200 rpm, and extruding pelletization obtains wire rod master batch, and gained pellet is passed through wire rod machine
It is distracted into 3D printing wire rod, wire rod machine parameter are as follows: 160 DEG C of an area, two 170 DEG C of areas, three 170 DEG C of areas, four 160 DEG C of areas, revolving speed are
50 rpm, the silk cooling by water of extrusion by traction machine travel and control wire vent line footpath 1.75mm, and obtaining can pore-creating wire rod；
(2) 10kg PETG is passed through into wire rod machine travel into 3D printing wire rod, wire rod machine parameter are as follows: 200 DEG C of an area, two areas 210
DEG C, three 200 DEG C of areas, four 200 DEG C of areas, revolving speed is 50 rpm, and the silk cooling by water of extrusion by traction machine travel and controls wire vent
Line footpath 1.75mm obtains high light transmission wire rod；
(3) by more material 3D printer integrations print, by obtained in step (1) can pore-creating wire rod be printed as device side
Frame, 180 DEG C of print temperature, high light transmission wire rod obtained in step (2) prints upper and lower panel, and 230 DEG C of print temperature, then in device
Inside loads 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2Post package obtains dendritic phthalocyanine@SiO2Photocatalytic device.
Embodiment 3
(1) by 7kg PBAT, 3kg Na2CO3It is granulated after mixing by screw rod melting extrusion, double screw extruder parameter are as follows: one
80 DEG C of area, two 90 DEG C of areas, three 100 DEG C of areas, four 110 DEG C of areas, five 120 DEG C of areas, six 130 DEG C of areas, seven 135 DEG C of areas, eight 130 DEG C of areas,
Nine 120 DEG C of areas, 110 DEG C of die head, revolving speed is 200 rpm, and extruding pelletization obtains wire rod master batch, and gained pellet is passed through wire rod machine
It is distracted into 3D printing wire rod, wire rod machine parameter are as follows: 120 DEG C of an area, two 130 DEG C of areas, three 130 DEG C of areas, four 120 DEG C of areas, revolving speed are
50 rpm, the silk cooling by water of extrusion by traction machine travel and control wire vent line footpath 1.75mm, and obtaining can pore-creating wire rod；
(2) 10kg TPU is passed through into wire rod machine travel into 3D printing wire rod, wire rod machine parameter are as follows: 160 DEG C of an area, two 170 DEG C of areas,
Three 170 DEG C of areas, four 160 DEG C of areas, revolving speed are 50 rpm, and the silk cooling by water of extrusion by traction machine travel and controls out silk thread
Diameter 1.75mm obtains high light transmission wire rod；
(3) by more material 3D printer integrations print, by obtained in step (1) can pore-creating wire rod be printed as device side
Frame, 130 DEG C of print temperature, high light transmission wire rod obtained in step (2) prints upper and lower panel, and 180 DEG C of print temperature, then in device
Inside loads 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2Post package obtains dendritic phthalocyanine@SiO2Photocatalytic device.
Embodiment 4
It is granulated after 8 kg PBS, 2kg PVA are mixed by screw rod melting extrusion, double screw extruder parameter are as follows: 70 DEG C of an area,
Two 80 DEG C of areas, three 90 DEG C of areas, four 100 DEG C of areas, five 100 DEG C of areas, six 110 DEG C of areas, seven 110 DEG C of areas, eight 100 DEG C of areas, nine areas 100
DEG C, 90 DEG C of die head, revolving speed is 150 rpm, and extruding pelletization obtains wire rod master batch, by gained pellet by wire rod machine travel at 3D
Print wire rod, wire rod machine parameter are as follows: 100 DEG C of an area, two 110 DEG C of areas, three 110 DEG C of areas, four 100 DEG C of areas, revolving speed are 30 rpm, are squeezed
Silk cooling by water out by traction machine travel and controls wire vent line footpath 1.75mm, and obtaining can pore-creating wire rod；
(2) 8kg PETG, 2kgTPU are passed through into wire rod machine travel into 3D printing wire rod, wire rod machine parameter are as follows: 200 DEG C of an area, two
210 DEG C of area, three 200 DEG C of areas, four 200 DEG C of areas, revolving speed are 50 rpm, and the silk cooling by water of extrusion by traction machine travel and is controlled
Silk thread diameter 1.75mm is produced, high light transmission wire rod is obtained；
(3) by more material 3D printer integrations print, by obtained in step (1) can pore-creating wire rod be printed as device side
Frame, 110 DEG C of print temperature, high light transmission wire rod obtained in step (2) prints upper and lower panel, and 220 DEG C of print temperature, then in device
Inside loads 1-3 and loads SiO for aryl oxide dendritic phthalocyanine complex2Post package obtains dendritic phthalocyanine@SiO2Photocatalytic device.
Note: 1-3 used in above-described embodiment 1-4 loads SiO for aryl oxide dendritic phthalocyanine complex2Before inventor
" 1-3 loads SiO for aryl oxide dendritic phthalocyanine complex to the patent of invention of phase authorization2The preparation method of visible-light photocatalyst and
The product that its application " (ZL2014108005249) prepares, specific product is using Patent No. 2014108005249
The product that any preparation method in the disclosed i.e. following specific example 1-3 of specification is prepared into, the specific steps are as follows:
The 1-3 loads SiO for aryl oxide dendritic phthalocyanine complex2The preparation method of visible-light photocatalyst, including it is as follows
Step:
(1) configure containing volume fraction be 70%~95% isopropanol water solution or volume fraction be 70%~95% ethyl alcohol it is water-soluble
50~80 mL of mother liquor of liquid；
(2) concentrated ammonia liquor is added into the solution of step (1) and adjusts pH value 7~12, water-bath item of the mixed solution at 30 DEG C~70 DEG C
It is uniformly mixed under part；
(3) it is the 1- that 0.2 milliliter~1.5 milliliters of concentration are 0.001~0.02 mol/L that volume is added into the solution of step (2)
The n,N-Dimethylformamide stock solution of 3 generation aryl oxide dendritic phthalocyanine complexes is uniformly mixed it after stirring；
(4) ethyl orthosilicate is added into the solution of step (3), continuing 4~12 h of stirring is fully hydrolyzed it, finally by solution
Filtering, washing, catalyst required for 60 DEG C~110 DEG C drying to obtain.
Above-mentioned 1-3 is zinc, copper, cobalt or iron for the central atom in aryl oxide dendritic phthalocyanine complex.
Specific example 1
(1) 8 milliliters of distilled water are added in 50 milliliters of isopropanol, are stirred evenly under 65 DEG C of water bath conditions；
(2) 1 milliliter of concentrated ammonia liquor and 1 milliliter of 1-3 are added into mixed solution, and for aryl oxide dendritic phthalocyanine complex, (center is former
Son is zinc) stock solution (0.02 mol/L), continues to stir 5 min；
(3) ethyl orthosilicate of 8 mL is added into solution, continuing 12 h of stirring is fully hydrolyzed it, finally solution is filtered,
Washing (isopropanol wash 3 times 10 milliliters every time, 10 milliliters every time of distillation water washing 5 times), solid is dried under the conditions of 70 DEG C
It is dry, required 1-3, which is obtained, for aryl oxide dendritic phthalocyanine complex (central atom is zinc) loads SiO2Catalyst.
Specific example 2
(1) 10 milliliters of distilled water are added in 50 milliliters of dehydrated alcohol, are stirred evenly under 65 DEG C of water bath conditions；
(2) 1 milliliter of concentrated ammonia liquor and 0.5 milliliter of 1-3 are added into mixed solution for aryl oxide dendritic phthalocyanine complex (center
Atom is zinc) stock solution (0.01 mol/L), continues to stir 5 min；
(3) ethyl orthosilicate of 8 mL is added into solution, continuing 8 h of stirring is fully hydrolyzed it, finally filters solution, washes
Wash (isopropanol wash 3 times 10 milliliters every time, 10 milliliters every time of distillation water washing 5 times), solid is dried under the conditions of 70 DEG C
It is dry, required 1-3, which is obtained, for aryl oxide dendritic phthalocyanine complex (central atom is zinc) loads SiO2Catalyst.
Specific example 3
(1) 8 milliliters of distilled water are added in 50 milliliters of isopropanol, are stirred evenly under 65 DEG C of water bath conditions；
(2) be added into mixed solution 0.46 milliliter of concentrated ammonia liquor and 1 milliliter of 1-3 for aryl oxide dendritic phthalocyanine complex (in
Heart atom is zinc) stock solution (0.02 mol/L), continues to stir 5 min；
(3) ethyl orthosilicate of 8 mL is added into solution, continuing 12 h of stirring is fully hydrolyzed it, finally solution is filtered,
Washing (isopropanol wash 3 times 10 milliliters every time, 10 milliliters every time of distillation water washing 5 times), solid is dried under the conditions of 70 DEG C
It is dry, obtain required catalyst.
Above-mentioned specific embodiment is the further description to the present patent application, but the claims in the present invention are protected
Range be not limited to range described in embodiment, it is all using equivalent replacement or the technical solution of equivalent deformation,
Fall in the protection scope of the claims in the present invention.
Claims (6)
1. a kind of dendritic phthalocyanine@SiO2The preparation method of photocatalytic device, which comprises the following steps:
(1) it is granulated after according to the ratio mixing plastic basis material, water-soluble pore creating material by screw rod melting extrusion, gained pellet is passed through
For wire rod machine travel at 3D printing wire rod, obtaining can pore-creating wire rod；
(2) high light transmission resin is granulated by screw rod melting extrusion, by gained pellet by wire rod machine travel at 3D printing wire rod,
Obtain high light transmission wire rod；
(3) by more material 3D printer integrations print, by obtained in step (1) can pore-creating wire rod be printed as device side
Frame, high light transmission wire rod obtained in step (2) is printed as the upper and lower panel of device, then is formed between the upper and lower panel of device
Internal cavities in load 1-3 for aryl oxide dendritic phthalocyanine complex load SiO2Post package obtains 3D printing photocatalytic device, can
The device frame that pore-creating wire rod is printed as can form porous into the water, realize the free entry and exit of dye molecule, and can prevent
Powder photocatalysis diffusion solves the problems, such as difficult withdrawal.
2. a kind of dendritic phthalocyanine@SiO according to claim 12The preparation method of photocatalytic device, which is characterized in that institute
The water-soluble pore creating material stated is one or more of in PVP, PVA, sucrose, NaCl, sodium carbonate.
3. a kind of dendritic phthalocyanine@SiO according to claim 12The preparation method of photocatalytic device, which is characterized in that institute
State the proportion of the plastic basis material and water-soluble pore creating material in step (1) are as follows: 60 ~ 95 parts of plastic basis material, water-soluble pore creating material 20 ~ 40
Part.
4. a kind of dendritic phthalocyanine@SiO according to claim 12The preparation method of photocatalytic device, which is characterized in that institute
The plastic basis material stated is selected from polylactic acid (PLA), polycaprolactone (PCL), two rouge of poly-succinic fourth (PBS), polyadipate/to benzene two
One of formic acid fourth diester (PBAT), acrylonitrile-butadiene-styrene (ABS) plastics (ABS), polypropylene (PP), polyethylene (PE)
Or it is a variety of.
5. a kind of dendritic phthalocyanine@SiO according to claim 12The preparation method of photocatalytic device, which is characterized in that institute
The high light transmission resin stated is selected from polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PETG), thermoplastic polyurethane
Elastomer rubber (TPU), polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PCTG), poly-methyl methacrylate
One of ester (PMMA) is a variety of.
6. dendritic phthalocyanine@SiO made from a kind of any preparation method of claim 1-52Photocatalytic device, feature
Be: the dendritic phthalocyanine@SiO2 photocatalytic device is applied to catalytic degradation phenol.
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| CN111645224A (en) * | 2020-06-18 | 2020-09-11 | 福建师范大学 | Preparation method of 3D printing self-suspension photocatalytic device |
| CN111825871A (en) * | 2020-06-18 | 2020-10-27 | 福建师范大学 | Preparation method of waste aluminum-plastic-based 3D printing photocatalytic device |
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| CN109878069B (en) | 2020-11-24 |
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